Minute structure and information recording medium

ABSTRACT

There is disclosed a minute structure including a sulfur compound and a silicon oxide. There is also disclosed a write-once information recording medium including a substrate and a recording layer formed of a mixed inorganic material and deposited on the substrate, wherein the mixed inorganic material contains a sulfur compound and a silicon oxide.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a minute structure and a write-once (WORM, orwrite-once read-many) information recording medium.

2. Description of the Related Art

Recently, the research and development of minute structures with a sizeranging from nanometer scale to micrometer scale is carried out in manyfields including nanophotonics, high-density recording media, opticalelements, and biochemical chips. What is indispensable to those devicesutilizing the opto-electronics is a material which is opticallytransparent in a visible light region and has little optical loss. Forthis reason, the research and development of a technology for producinga minute structure from a transparent material is carried out briskly.

Zinc oxide is optically transparent in a visible light region and has aproperty to absorb ultraviolet light. Zinc oxide is used for thepurposes, such as LED, transparent transistor, UV cut material,electrophotography, etc.

Examples of the method of forming a zinc oxide may include thesputtering method, the ion plating method (refer to Japanese Laid-OpenPatent Application No. 2006-117462), and the thermal decomposition of aprecursor (refer to Japanese Laid-Open Patent Application No.2007-022851).

Generally, when producing quantum wires, dots, etc. having aone-dimensional or two-dimensional periodical minute structure, any ofan electron beam exposure system, an ion beam exposure system, and astepper exposure system is used. However, these exposure systems requirethe vacuum source and they are expensive, and the production costbecomes high. For this reason, it is desired that simple patterning isperformed with low cost and a periodical minute structure is produced.

If a periodical structure in which minute structures are arrangedregularly is irradiated by light, unique phenomena, such as the photonicband effect, will arise. Applications of the periodical structure to anoptical waveguide, an optical filter, an optical switch, a low thresholdlaser, etc. which utilize light resonance or photon inclusion, areexpected. Moreover, it is known that a periodical structure in whichminute structures are arranged regularly at intervals below thesubwavelength serves to prevent the Fresnel reflection and exhibitsnon-reflection characteristics by the structure called moth-eyestructure (refer to OPTICAL REVIEW, Vol. 10, No. 2, 2003, pages 63-73).

On the other hand, in the field of biotechnology, it is stronglydemanded to use a minute structure as a DNA chip in which molecules andatoms are selectively combined. The DNA chip enables the existence of agene which is the cause of sickness to be easily investigated, and isused for study on the gene and diagnosis of the sickness.

The DNA chip usually is composed of a thin substrate of silicon orglass, and a DNA (deoxyribonucleic acid) which constitutes the genewhich is the cause of sickness is stuck on the DNA chip. If the bloodtaken from the patient and processed is dropped on the DNA chip and thegene which is the cause of sickness exists in the blood, the DNA in theblood adheres to the DNA of the DNA chip. It is easily judged whetherthe patient is sick or not. If the behavior of gene is investigated,early detection of sickness and anticipation of the side effects ofdrugs will be attained. At the medical spots, the demands for geneticscreening grow quickly.

Moreover, as for metallic minute structures which are regularly arrangedin a two-dimensional formation, the application deployment utilizinginteraction of light and molecules by surface plasmon excitation isexpected.

The existing method of producing a minute structure and a periodicalstructure in which minute structures are arranged regularly, usesoptical lithography in a semiconductor microfabrication. Since theexisting method requires an expensive electron-beam lithography system,it has a problem of high cost. Moreover, the size of the minutestructure produced depends on the performance of the producingequipment.

On the other hand, a mask is produced and the existing method has anadvantage that it is suitable for mass production. However, it isunsuitable for a simple circuit design at a time of specification changeand a simple experiment at an experimental stage.

There is also known a method of producing a three-dimensional minutestructure or a three-dimensional photonic crystal using the 2-photonabsorption by a laser beam (refer to Japanese Laid-Open PatentApplications No. 2003-001599 and No. 2005-122002). However, theproduction needs much time and the material used is limited to the resinthat can be produced by a photopolymerization reaction. For this reason,a simple, inexpensive method of producing a minute structure which canimprove resource saving further is demanded.

The existing method of forming a reversal structure of a minutestructure or a periodical structure in which minute structures arearranged regularly uses emboss processing including an injectionmolding. In recent years, the nano imprint technology which accuratelytransfers a reversal structure of a nano-scale structure has beendeveloped. The nano imprint technology using photopolymerization orthermal polymerization can produce a reversal structure of a master moldwith sufficiently high accuracy, and it is suitable for mass production.When a reversal structure is used as a photonic crystal, a differenteffect from a master mold arises.

In recent years, attention is given to heat lithography as a low-costprocessing method which is more cost-effective than the microfabricationusing optical lithography. Heat lithography is a microfabricationtechnology utilizing the principle that when an endothermic layer isheated (which layer functions as a light absorption layer whenirradiated by a laser beam), the characteristics (light transmittance,refractive index, conductivity, chemistry corrosion resistance, etc.) ofthe heated part are changed. The temperature distribution of the areairradiated by light turns into Gaussian distribution, the area of thehigh-temperature region in the center of the distribution is about 1/10of the area of a light spot, and the characteristics of that area onlyare changed. Thus, fabrication of a minute pattern is possible.

Japanese Laid-Open Patent Application No. 2005-158191 discloses a methodof manufacturing an optical recording medium which includes at least astep of laminating a first dielectric layer, a light absorption layer,and a second dielectric layer one by one on a supporting substrate, astep of emitting a laser beam to record information, and a step ofremoving a non-recorded area of the second dielectric layer by wetetching, to form a convex part of the second dielectric layer.

In the method disclosed in Japanese Laid-Open Patent Application No.2005-158191, the convex part of the second dielectric layer formed has across section which is rectangular or in an inverse tapered shape, andsince the etching resistance is increased only in the vicinity of themaximum value in the heat distribution (Gaussian distribution), the sizeof the convex part is less than the diffraction limit of light. And theetching resistance of the 2nd dielectric layer on the light absorptionlayer where the laser light is absorbed improves and the convex part isformed. However, since there are many uses which require removal of thelight absorption layer, forming the convex part, without forming thelight absorption layer is demanded. There is also a problem that, whenforming a concave part in the second dielectric layer, the end of theconcave part is roughed.

An optical element having a subwavelength structure or a fine structureof photonic crystal is demanded in recent years. Application of suchfine structure is not limited to optical elements. For example, anorganic electro-luminescence (OEL) display or organic light-emittingdiode display (OLED) is a new generation light-emitting display using anorganic compound. When compared with the conventional display, the lightemitted by the OLED is bright and clear, the angle of field is large,the display is of thin type, and the operational temperature range isextensive. The OLED is observed as a display with the outstandingfeatures. Moreover, it is known that the luminous efficiency of OLED isimproved by combining it with a two-dimensional photonic crystalstructure. For example, refer to “M. Fujita, T. Ueno, T. Asano, S, Noda,H. Ohata, T. Tsuji, H. Nakada and N. Shimoji, Electronics Letters, Vol.39, p. 1750 (2003)”, “Y. Lee, S. Kim, J. Huh, G. Kim and Y. Lee, AppliedPhysics Letters, Vol. 82, p. 3779 (2003)”, “M. Kitamura, S. Iwamoto andY. Arakawa, Japanese Journal of Applied Physics, Vol. 44, p. 2844(2005)”, “K. Ishihara, M. Fujita, I. Matsubara, T. Asano and S, Noda,Japanese Journal of Applied Physics, Vol. 45, No. 7, p. L210 (2006)”,and “M. Fujita, K. Ishihara, T. Ueno, T. Asano, S, Noda, H. Ohata, T.Tsuji, H. Nakada and N. Shimoji, Japanese Journal of Applied Physics,Vol. 44, p. 3669 (2005)”.

Also in photoelectric conversion devices, such as solar cells, thenecessity for fine structure is known. The solar cells are grouped intodry-type solar cells formed of single crystal silicon, polycrystallinesilicon, amorphous silicone, etc. and wet-type solar cells, such asGraetzel cell or dye-sensitized solar cell. In the dye sensitized typesolar cell, titanium oxide is used as a semiconductor electrode.However, theoretically, solar cells using other oxide semiconductors maybe attained and various researches for the purposes are in progress.

SUMMARY OF THE INVENTION

According to one aspect of the invention, there is disclosed an improvedminute structure in which the above-described problems are eliminated.

According to one aspect of the invention, there is disclosed a minutestructure which can be easily formed by using the heat lithography.

According to one aspect of the invention, there is disclosed aminute-structure manufacturing method which can easily form a minutestructure by using the heat lithography.

According to one aspect of the invention, there is disclosed awrite-once information recording medium which can be produced with lowcost and can form a minute recording mark therein.

In an embodiment of the invention which solves or reduces one or more ofthe above-mentioned problems, there is disclosed a minute structurecomprising a sulfur compound and a silicon oxide.

The above-mentioned minute structure may be arranged so that the minutestructure is in any one of a convex configuration having a curvedsurface, a configuration in which a convex structure having a curvedsurface is formed on a cylinder structure, and a cylindricalconfiguration.

The above-mentioned minute structure may be arranged so that the minutestructure is in any one of a convex configuration having a curvedsurface, a configuration in which a convex structure having a curvedsurface is formed on a cylinder structure, and a configuration in whicha cylindrical cross section is formed continuously.

The above-mentioned minute structure may be arranged so that the sulfurcompound contains ZnS.

The above-mentioned minute structure may be arranged so that the sulfurcompound contains a first sulfur compound for raising an opticalabsorption ability to a light with a predetermined wavelength.

The above-mentioned minute structure may be arranged so that the sulfurcompound contains at least one of FeS and GeS₂.

The above-mentioned minute structure may be arranged so that the minutestructure further comprises a material for raising an optical absorptionability to a light with a predetermined wavelength.

The above-mentioned minute structure may be arranged so that thematerial for raising the optical absorption ability to the light withthe predetermined wavelength contains at least one of Al, Ag, Au, Cu,Zn, Pt, Sb, Te, Ge, Si, Bi, Mn, W, Nb, Co, Sr, Fe, In, Sn, Ni, Mo, Mg,and Ca.

The above-mentioned minute structure may be arranged so that the minutestructure further comprises an oxide of the material for raising theoptical absorption ability to the light with the predeterminedwavelength.

The above-mentioned minute structure may be arranged so that thematerial for raising the optical absorption ability to the light withthe predetermined wavelength contains at least one of a second sulfurcompound and a zinc compound.

The above-mentioned minute structure may be arranged so that thematerial for raising the optical absorption ability to the light withthe predetermined wavelength contains at least one of ZnTe, ZnSe, andMnS.

The above-mentioned minute structure may be arranged so that thematerial for raising the optical absorption ability to the light withthe predetermined wavelength contains a fluorescent material.

The above-mentioned minute structure may be arranged so that thefluorescent material is either CdSe or CdTe.

The above-mentioned minute structure may be arranged so that apercentage of content of the silicon oxide is in a range between 10 mol% and 30 mol %.

In an embodiment of the invention which solves or reduces one or more ofthe above-mentioned problems, there is disclosed a method ofmanufacturing a minute structure, the method comprising the steps of:forming a layer, containing a sulfur compound and a silicon oxide, on asubstrate; irradiating the layer containing the sulfur compound and thesilicon oxide by a laser beam; etching the layer irradiated by the laserbeam to form a minute structure, wherein the sulfur compound contains afirst sulfur compound for raising an optical absorption ability to alight with a predetermined wavelength, or the layer containing thesulfur compound and the silicon oxide further contains a material forraising the optical absorption ability.

In an embodiment of the invention which solves or reduces one or more ofthe above-mentioned problems, there is disclosed a write-onceinformation recording medium comprising: a substrate; and a recordinglayer formed of a mixed inorganic material and deposited on thesubstrate, wherein the mixed inorganic material contains a sulfurcompound and a silicon oxide.

The above-mentioned write-once information recording medium may bearranged so that the mixed inorganic material further contains aninorganic material which is different from the sulfur compound and thesilicon oxide and chosen from among a metal, a semimetal, and asemiconductor, and the recording layer has an optical absorption abilityto a light with a predetermined wavelength which is larger than anoptical absorption ability of a recording layer of a same thicknesswhich does not contain the inorganic material.

The above-mentioned write-once information recording medium may bearranged so that the write-once information recording medium furthercomprises a dielectric layer and a reflection layer which are depositedon the substrate.

The above-mentioned write-once information recording medium may bearranged so that the inorganic material contains an element whichconstitutes the sulfur compound and the silicon oxide.

The above-mentioned write-once information recording medium may bearranged so that the inorganic material contains at least one elementchosen from among Al, Ag, Au, Cu, Zn, Pt, Sb, Te, Ge, Si, Bi, Mn, W, Nb,Co, Sr, Fe, In, Sn, Ni, Mo, Mg, Ca, Pb, and Ba.

According to the embodiments of the invention, it is possible to providea minute structure which can be easily formed by using the heatlithography, and a minute-structure manufacturing method which caneasily form a minute structure by using the heat lithography.

According to the embodiments of the invention, it is possible to providea patterning method of a substrate using the minute structure, and astructure, an information recording medium, a master substrate, anoptical element, an optical communication device, a DNA chip, a lightemitting device, a photoelectric transducer and an optical lens whichinclude the minute structure.

According to the embodiments of the invention, it is possible to providea write-once information recording medium which can be produced with lowcost and can form a minute recording mark therein.

BRIEF DESCRIPTION OF THE DRAWINGS

Other objects, features and advantages of the invention will be apparentfrom the following detailed description when reading in conjunction withthe accompanying drawings.

FIG. 1A and FIG. 1B are diagrams showing the composition of aninformation recording medium of the embodiment 1.

FIG. 2A, FIG. 2B, FIG. 2C, and FIG. 2D are cross-sectional views forexplaining the method of manufacturing the information recording mediumof the embodiment 1.

FIG. 3A and FIG. 3B are diagrams showing the composition of aninformation recording medium of the embodiment 2.

FIG. 4A and FIG. 4B are diagrams showing scanning electron microscopephotographs of the minute structure (4.5 mW pulsed light output).

FIG. 5A and FIG. 5B are diagrams showing scanning electron microscopephotographs of the minute structure (5.0 mW pulsed light output).

FIG. 6A and FIG. 6B are diagrams showing scanning electron microscopephotographs of the minute structure (5.5 mW pulsed light output).

FIG. 7A and FIG. 7B are diagrams showing scanning electron microscopephotographs of the minute structure (6.0 mW pulsed light output).

FIG. 8A and FIG. 8B are diagrams showing scanning electron microscopephotographs of the minute structure (6.4 mW pulsed light output).

FIG. 9A and FIG. 9B are diagrams showing scanning electron microscopephotographs of the minute structure (7.0 mW pulsed light output).

FIG. 10 is a diagram for explaining the relationship between the pulsedlight output and the maximum diameter of the minute structure.

FIG. 11A, FIG. 11B, FIG. 11C and FIG. 11D are cross-sectional diagramsof the minute structure in stage I, stage II, stage III and stage IV,respectively.

FIG. 12A and FIG. 12B are diagrams showing the composition of an opticalnonreflection film of the embodiment 4.

FIG. 13A and FIG. 13B are diagrams showing the composition of an opticalwaveguide of the embodiment 5.

FIG. 14A and FIG. 14B are diagrams showing the composition of an opticalfilter of the embodiment 6.

FIG. 15 is a diagram showing the composition of a master substrate ofthe embodiment 7.

FIG. 16A, FIG. 16B, FIG. 16C, FIG. 16D, FIG. 16E and FIG. 16F arecross-sectional diagrams for explaining the method of manufacturing themaster substrate of FIG. 15.

FIG. 17 is a cross-sectional diagram showing another example of theminute structure of the embodiment 7.

FIG. 18A and FIG. 18B are diagrams showing the composition of an opticalnonreflection film of the embodiment 8.

FIG. 19A and FIG. 19B are diagrams showing the composition of an opticalnonreflection film of the embodiment 9.

FIG. 20 is a cross-sectional diagram showing another example of theoptical nonreflection film of the embodiment 9.

FIG. 21 is a diagram showing the composition of an information recordingmedium of the embodiment 10.

FIG. 22A and FIG. 22B are diagrams showing the composition of an opticalwaveguide of the embodiment 11.

FIG. 23 is a cross-sectional diagram showing the composition of anoptical filter of the embodiment 12.

FIG. 24 is a cross-sectional diagram showing another example of theoptical filter of the embodiment 12.

FIG. 25A, FIG. 25B, FIG. 25C and FIG. 25D are diagrams showing scanningelectron microscope photographs of the minute structure of theembodiment 13.

FIG. 26 is a diagram for explaining the relationship between the pulsedlight output and the outer diameter or the inner diameter of the minutestructure.

FIG. 27A and FIG. 27B are diagrams showing scanning electron microscopephotographs of another example of the minute structure of the embodiment13.

FIG. 28 is a diagram showing a scanning electron microscope photographof another example of the minute structure of the embodiment 13.

FIG. 29A, FIG. 29B, FIG. 29C and FIG. 29D are diagrams showing scanningelectron microscope photographs of the minute structure of theembodiment 15.

FIG. 30A and FIG. 30B are diagrams showing scanning electron microscopephotographs of another example of the minute structure of the embodiment15.

FIG. 31 is a diagram for explaining wavelength division multiplexcommunication.

FIG. 32 is a perspective view showing the composition of a polarizationseparator element of the embodiment 17.

FIG. 33A, FIG. 33B, FIG. 33C and FIG. 33D are cross-sectional diagramsfor explaining the method of manufacturing the polarization separatorelement of the embodiment 17.

FIG. 34A and FIG. 34B are diagrams showing scanning electron microscopephotographs of the polarization separator element (3.5 mW pulsed lightoutput) of the embodiment 17.

FIG. 35 is a diagram showing the wavelength dependency of thetransmittance to S polarized light of the polarization separator elementof the embodiment 17.

FIG. 36A and FIG. 36B are diagrams showing scanning electron microscopephotographs of the polarization separator element (2.5 mW pulsed lightoutput) of the embodiment 17.

FIG. 37 is a diagram showing the wavelength dependency of thetransmittance to S polarized light of the polarization separator elementof the embodiment 17.

FIG. 38 is a perspective view showing the composition of an opticalfilter of the embodiment 18.

FIG. 39A, FIG. 39B, FIG. 39C and FIG. 39D are cross-sectional diagramsfor explaining the method of manufacturing the optical filter of theembodiment 18.

FIG. 40A and FIG. 40B are diagrams showing scanning electron microscopephotographs of the optical filter of the embodiment 18.

FIG. 41 is a diagram showing the wavelength dependency of thetransmittance to S polarized light of the optical filter of theembodiment 18.

FIG. 42A and FIG. 42B are cross-sectional diagrams showing thecomposition of an inorganic EL element of the embodiment 19.

FIG. 43 is a cross-sectional diagram showing the composition of adye-sensitized solar cell of the embodiment 20.

FIG. 44A and FIG. 44B are diagrams showing the composition of anaspheric optical lens of the embodiment 21.

FIG. 45A and FIG. 45B are diagrams showing the composition of an opticalinformation recording medium in an embodiment of the invention.

FIG. 46A and FIG. 46B are diagrams showing scanning electron microscopephotographs of samples of the optical information recording medium inwhich the recording layer is irradiated by a laser beam.

FIG. 47A and FIG. 47B are diagrams showing the composition of an opticalinformation recording medium in an embodiment of the invention.

FIG. 48A and FIG. 48B are diagrams showing the composition of a mastersubstrate in an embodiment of the invention.

FIG. 49 is a diagram showing the composition of a quartz substrate onwhich recording pits are formed.

FIG. 50A and FIG. 50B are diagrams showing the composition of a mastersubstrate for an optical nonreflection film in an embodiment of theinvention.

FIG. 51 is a diagram showing the composition of a quartz substrate onwhich a pattern is formed.

FIG. 52A and FIG. 52B are diagrams showing scanning electron microscopephotographs of samples of an optical information recording medium in anembodiment of the invention in which a recording layer formed of a mixedinorganic material is irradiated by a laser beam.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

A description will be given of embodiments of the invention withreference to the accompanying drawings.

The minute structure of the embodiment 1 of the invention includes amixed component which contains at least one kind of a sulfur compound(called material A) and at least one kind of a silicon oxide (calledmaterial B). The sintering by heat when forming the minute structure ispromoted as the material A is contained, and patterning using etching ispossible as the material B is contained. Design of an opticalnonreflection film or a photonic crystal in which the configuration ofthe minute structure reflected is possible, and the refractive index ofminute structure can be easily adjusted.

Examples of material A may include ZnS, CaS, BaS, CdS, K2S, Ag2S, GeS,CoS, Bi2S3, PbS, Na2S, Cu2S, CuS, Al2S3, Sb2S3, SmS, PbS, Na2S, LiS,SiS, SiS2, and any combination including two or more compounds may beused. Among these, ZnS is preferred since it is easily mixed withmaterial B and it is available as a sputtering target with a low price.Since the crystallinity improves with optical irradiation or heating bya laser beam, a difference in the etching resistance between theirradiated area and the non-irradiated area arises. The minute structurecan be produced by using this principle. Adjustment of the refractiveindex of minute structure is also attained. Therefore, the processing byheat lithography is possible and an optical element and an informationrecording medium having the feasible optical property can be obtained.

The material B is primarily SiO2, and SiO may be contained therein. SiOmay be produced due to the oxygen deficiency at the time of forming atarget or at the time of forming a mixed material layer.

The minute structure of the embodiment 2 of the invention includeseither a mixed component which contains a sulfur compound (calledmaterial A′), the material B and a material for raising an opticalabsorption ability to a light with a predetermined wavelength (calledmaterial C), or a mixed component which contains a material A′ forraising an optical absorption ability to a light with a predeterminedwavelength and the material B. The minute structure can be formed on asubstrate having no light absorption layer by using heat lithography.

It is preferred that the size of the minute structure is in a rangebetween several tens of nanometers and several hundreds of nanometers.This size is equivalent to the size of a recording mark of ahigh-density-recording medium, or the size of a constitutional unit of aperiodical structure. In the latter case, the material A′ for raisingthe optical absorption ability to the light with the predeterminedwavelength may be used together with the material C or a material A′which does not raise the optical absorption ability to the light withthe predetermined wavelength.

A description will be given of the optical absorption ability. Asubstance having an optical absorption ability reflects light andsimultaneously absorbs light. The amount of absorption of light variesdepending on depth z by which light invades into the substance, and theamount of absorption of light is determined by its extinctioncoefficient k. The extinction coefficient k is represented by thefollowing Beer's law:I=Ioexp(−αz), α=4πk/λ

where I denotes the intensity of light after penetrating the substance,Io denotes the intensity of light before penetrating the substance, αdenotes the absorption coefficient, and λ denotes the wavelength oflight.

Namely, if the depth (the thickness of the substance) by which lightinvades into the substance increases, the substance absorbs a largeramount of light and the intensity of light penetrated the substancedecreases. Raising the optical absorption ability according to theinvention means enlarging the extinction coefficient k of the minutestructure containing the material concerned from that of a minutestructure with the same thickness which does not contain the materialconcerned.

The wavelength dependency of the extinction coefficient k variesdepending on the material. For example, even when k of a certainmaterial is small in a visible light region, k of the same material islarge in an ultraviolet region. Taking this point into consideration, itis necessary to select the wavelength of a laser beam for irradiating amixed material. The wavelength of a laser beam used is not restricted,and any of a deep-ultraviolet laser light, a visible laser light, aninfrared laser light, etc. may be used. Especially, a red semiconductorlaser beam and a blue semiconductor laser beam are preferred since theyare inexpensive and irradiation of multiple pulsed light beam can beperformed. Examples of the light source used may include a visible lightlaser, an F₂ laser, an ArF laser, a KrF laser, etc. Among them, avisible light semiconductor laser is preferred since it can be obtainedwith low cost and can be used easily.

Measurement of an extinction coefficient k and a refractive index n canbe carried out using a spectroscopic ellipsometer. The extinctioncoefficient k, together with the refractive index n, varies inaccordance with the wavelength of light. For example, in the case ofZnS—SiO2 (the molar ratio: 80:20), with respect to a 405 nm laser light(blue), n is about 2.33 and k is about 1×10⁻³, with respect a 350 nmlaser light (ultraviolet), n is about 2.33 and k is about 1×10⁻², andwith respect to a 680 nm laser light (red), n is about 2.16 and k isabout 1×10⁻⁸. Addition of the material C to the minute structure allowsthe refractive index n and the extinction coefficient k to be adjusted.

Examples of the material A′ other than the material A may be thematerial for raising the optical absorption ability, such as FeS andGeS2. Two or more kinds of the material A′ may be used in combination.Among them, ZnS is preferred since it is easily mixed with the materialB and can be obtained with low cost as a sputtering target. ZnS isalmost transparent in a visible light region, and addition of thematerial C to the minute structure will allow adjustment oftransmittance to visible light of the minute structure.

An example of the minute structure formed of a mixed material containingZnS (material A′), SiO2 (material B) and a metal or semiconductor(material C) as an example of the minute structure of the invention willbe explained.

SiO₂ has little etching resistance to hydrofluoric acid and it reacts inaccordance with the formula: SiO₂+6HF−> H₂SiF₆+H₂O. The layer formed ofthe mixed material is etched in a hydrofluoric acid, and it absorbsvisible laser light. The etching resistance to hydrofluoric acid of theheated mixed material improves, and it remains non-etched and a minutestructure is left.

Specifically, if the mixed material absorbs a visible laser light havingmore than a given output power and it is heated, a kind ofcrystallization of ZnS and SiO2 arises and the etching resistance tohydrofluoric acid improves. If the percentage of content of ZnS in themixed material at this time is less than 60 mol %, the etchingresistance to hydrofluoric acid may be inadequate.

SiO2 is required in order to etch the mixed material. However, if thepercentage of content of SiO2 in the mixed material is less than 10 mol%, it shows some etching resistance to hydrofluoric acid even when itdoes not absorb visible laser light. If the percentage of content ofSiO2 in the mixed material exceeds 30 mol %, a minute structure may notbe left. ZnS—SiO2 penetrates a visible light. If the mixed materialabsorbs a visible light and does not contain a material C for generatingheat, heating may be inadequate even when it is irradiated by a visiblelaser. If an organic material is used as the material C, heating may beinadequate. This may be because addition of the organic material in thiscase does not allow the extinction coefficient k to increase.

For this reason, it is preferred that the material C is a semiconductormaterial or a metallic material. Although the layer which is formed of amixed material can be formed by the sputtering method, it may use forand carry out the weld slag of the mixed target other than simultaneousweld slag. A mixed target is producible material A′ and by mixing thepowder of material B and material C, and making it sinter.

It is preferred that the material C contains either of the zinc compoundand the sulfur compound different from the material A′. When ZnS is usedas the material A′, either the sulfur or zinc contained in the materialA′ is contained in the material C which makes the configuration of theend of the minute structure smooth. Examples of the material C mayinclude ZnTe, ZnSe, MnS, etc. although these are not restrictive butthey can receive supply as a sputtering target. Two or more kinds ofthem may be used in combination.

Examples of the material C may include Al, Ag, Au, Cu, Zn, Pt, Sb, Te,Ge, Si, Bi, Mn, W, Nb, Co, Sr, Fe, In, Sn, Ni, Mo, Mg, Ca, etc., and twoor more kinds of them may be used in combination. Examples of suchmaterial C may include any of alloys, such as InSb, AgInSbTe, GeSbTe,ZnMgTe, CsZnTe, SbZn, and the compounds, such as ZnMgSSe, ZnCrO4,ZnZrO3, ZnWO4, ZnTiO3, Zn3N2, ZnF2, ZnSnO3, and ZnMoO4. Such materialscan be easily obtained as a sputtering target, and can adjust therefractive index of minute structure.

It is preferred that the material C contains a fluorescent material. Theposition of the minute structure can be checked by detecting thefluorescence which is emitted from the minute structure when it isirradiated by an ultraviolet light or visible light. For this reason, aspecific part can be detected using fluorescence detection of afluorescent semiconductor quantum dot, and the use as an informationrecording medium is possible. As a fluorescent material, CdSe, CdTe,etc. are mentioned and two or more kinds may be used together. Such afluorescent material has a high fluorescent characteristic, and it canobtain it easily.

When it is irradiated by a laser beam, the material C may oxidize. Thegrade in which the material C oxidizes is based on the irradiationconditions (pulsed light output, pulse width) of a laser beam, the kindof material C, the composition of material A′, material B, and materialC, etc.

However, if material A′ is used on a Si substrate, an electric furnaceis used after carrying out multitarget sputtering of material B and thematerial C, and for 30 minutes heat curing (annealing) is carried out athundreds of times, the peak of the oxide of material C will be seen inan oblique incidence X-ray diffraction experiment.

For example, when a 200 nm thick film of ZnS, SiO2 and Zn is formed on aSi substrate, the peak of ZnO is not seen, but the peak of ZnO is seenwhen annealing is performed for 30 minutes at 500 degrees C. It isconceivable that at least a part of Zn (material C) was oxidized andthis was set to ZnO.

Similarly, in the case of ZnS, SiO2 and Mn, the peak of Mn3O4 is notseen before annealing, but as for after annealing, the peak of Mn3O4 isseen. When it is irradiated by a laser beam at this time, it is notclear what extent the irradiation portion of the laser beam is heatedto, and by what speed it is cooled. However, the material C in apredetermined quantity may be oxidized also in the minute structureetched by a hydrofluoric acid. For this reason, in the followingembodiments, although it is illustrated as the composition of minutestructure is the same as before laser beam irradiation, there is also acase in which the minute structure contains the oxide of material C.Thus, if the material C in the predetermined quantity is oxidized, thehardness of the minute structure can be raised. Specifically, thehardness of the minute structure measured using the minute probe becomeshigher than the hardness of the thin film before forming minutestructure. At this time, optical properties, such as transmittance and arefractive index, also change with oxidization of material C. Althoughthe configuration of the minute structure of the invention is notrestrictive, it may be a convex configuration which has a curved surfacesuch as a hemispherical surface. If the microfabrication of such minutestructure is carried out using an X-ray or optical lithography, it wouldbe expensive. The manufacture of the minute structure is attained withlow cost using the heat lithography, and it is applicable to an opticalelement or a master mold of nano-imprinting. An optical element isobtained by forming distribution of physical characteristics or chemicalproperties in the minute structure.

An end of a minute structure of a convex configuration which has acurved surface becomes smooth and the minute structure has a curvedsurface. However, a sharp edge or a flat side surface may arisedepending on the manufacturing conditions. In three dimensions, the areawhich has a curved surface exists from the configuration of the minutestructure following the heat distribution of the laser beam mainlyirradiate the layer which is formed of a mixed material.

Since the area where the laser beam is not irradiated by performing wetetching by a hydrofluoric acid is removed, minute structure serves as aconvex configuration. For this reason, if it transfers usingphoto-curing type resin etc., the pattern of concave shape will beformed in the transferred substrate.

The minute structure of the invention may be in a configuration in whicha convex structure which has a curved surface, such as a hemisphericalsurface, is formed on a cylinder structure. Since such minute structurehas the two-step structure, the gap between the convex structures havingadjoining curved surfaces can be maintained and it is possible toseparate recording marks clearly in the information recording mediumusing fluorescence. The optical nonreflection film and photonic crystalreflecting such form can also be designed, and a refractive index can beadjusted. In the photolithography in which a sensitization part carriesout a chemical change, the minute structure of such form isunproducible.

The minute structure of the invention may be in a cylindricalconfiguration. If microfabrication is carried out using an X-ray oroptical lithography, the manufacture of the structure would beexpensive. However, the manufacture of the structure can be attainedwith low cost using the heat lithography, and it is applicable also toan optical element or a master mold of nano-imprinting. In addition, anoptical nonreflection film and photonic crystal which reflects suchconfiguration can also be designed, and the refractive index can beadjusted. If the photolithography in which the sensitization part showsa chemical change is used, it is difficult to produce the minutestructure having such configuration.

In the invention, the diameter of the minute structure can be changedfrom a light spot size to the size of about ¼ of the spot size bychanging the pulsed light output and pulse width (irradiation time). Forexample, when a laser beam with the wavelength of 405 nm is focusedusing an objective lens with the NA of 0.85, the diameter of the minutestructure can be changed to any in a range of 80-400 nm.

The minute structure of the invention may be in any one of a convexconfiguration having a curved surface, a configuration in which a convexstructure having a curved surface is formed on a cylinder structure, anda cylindrical configuration in which the cross section is formedcontinuously. Such linear minute structure can be formed by irradiatingcontinuously the layer formed of a mixed material, and can be applied toa diffraction grating, a DNA chip, etc.

The smoothness of the end of the minute structure can be estimated bythe line edge roughness (LER) of the linear minute structure which isformed by carrying out continuous irradiation of a laser beam. In a casein which the minute structure is used as a resist and a substrate isetched. In such a case, the minute structure of the invention hascharacteristics different from those of a macromolecule resist used inelectron-beam lithography. In the macromolecule resist, themacromolecule itself has a size of several nanometers as the patternbecomes minute, the LER of the resist is also set to several nanometers.

On the other hand, LER can be set to 1 nm or less in the minutestructure of the invention. In recent years, the term “LER” is beingmodified to the “LWR” (line width roughness) in the InternationalTechnology Roadmap for Semiconductor (ITRS). Although the measurementcriteria of LER is not defined strictly, the LER according to theinvention is determined such that the measurement line length is set to2 micrometers, the measurement gap is set to 10 nm, and the LER isdetermined from 3σ of a straight line by the minimum square method.

The minute structure of the invention is applicable to an informationrecording medium, a master substrate, an optical element, a magneticrecording medium, a DNA chip, a biosensor, a DNA computer, a DNA memory,a biomolecule integrated device, etc.

The method of manufacturing the minute structure of the inventionincludes a step of forming on a substrate a layer which is formed ofmaterial A′ and a mixed material containing material B and material C, astep of irradiating locally the layer formed of the mixed material by alaser beam, and a step of performing etching of the layer formed of themixed material and irradiated by the laser beam. For this reason, aminute structure with a smooth end can be produced through a wet or dryetching of the mixed material which is locally heated and has theetching resistance changed.

A structure in which the minute structures of the invention are formedcan be manufactured. Although heat may be locally applied instead ofirradiating a laser beam locally, since a laser beam excels in respectof directivity and stability, it is preferred to use a laser beam inview of the production accuracy.

The patterning method of the substrate of the invention includes a stepof forming on a substrate a minute structure containing material A′,material B and material C, and a step which performing etching of thesubstrate using the minute structure as a mask. At this time, the minutestructure used as a mask may be removed if needed. Thus, the substratein which a pattern is formed is applicable to a master substrate, anoptical element, a DNA chip, a light emitting device, a photoelectrictransducer, etc.

Although the structure of the invention has the minute structures of theinvention on the substrate, it is preferred that the structure of theinvention has the area (called periodic area) in which the minutestructures are arranged periodically. The optical filter and opticalswitch using the photonic band gap which reflects the light of aspecific wavelength band by the periodic area can be obtained.

It is preferred that, in the periodic area, the transmittance to thelight of a predetermined wavelength band is higher than that in a casewhere the minute structures are not arranged. Thereby, the opticalnonreflection film by the moth-eye structure in which nonreflectioncharacteristics are shown to the light of a predetermined wavelengthband can be obtained.

If the structure of the invention includes an area (called a non-periodarea) in which the minute structures are not arranged, an informationrecording medium using distinction of the periodic area and thenon-period area, and an optical waveguide which includes the non-periodarea in the periodic area and uses the photonic band gap which reflectsthe light of a specific wavelength band by the periodic area can beobtained. In the minute structure of the invention used for aninformation recording medium, a fluorescent material is contained in thematerial C.

The pattern formed on the substrate by using the patterning method ofthe substrate of the invention may be transferred and reproduced, andthe minute structure formed on the substrate may be transferred andreproduced. When reproducing, the pattern and the minute structure canbe transferred into the material containing resin as the mainingredients through the nano imprinting technology. Such method can beused when manufacturing a master substrate, an optical element, a DNAchip, a light emitting device, a photoelectric transducer, an opticallens, etc.

The master substrate of the invention is manufactured using thestructure which includes the area in which the minute structures of theinvention are arranged periodically on the substrate. For this reason,the manufacture cost of the master substrate of the invention can belower than the master substrate using the conventional opticallithography, and the recording pattern can be made clear. Such mastersubstrate can be used when manufacturing an optical informationrecording medium, etc.

The optical element of the invention is manufactured using the structurewhich includes the area in which the minute structures of the inventionare arranged periodically on the substrate. Examples of the opticalelement may include a diffraction grating, a polarization separatorelement, an optical filter, an optical switch, an optical nonreflectionfilm, and an optical waveguide.

The optical element of the invention is applicable to a known opticalcommunication device, such as a wavelength multiplexing device, used forwavelength multiple telecommunications. As shown in FIG. 31, in thewavelength multiple telecommunication which communicates the lightsignals of several different wavelengths (λ1, λ2, and λ3) using oneoptical fiber 301, a set of transmitters 311, 312, and 313 and a set ofreceivers 321, 322, and 323 are used for each of the multiplewavelengths. In order to make the transmission path broad bandwidth, anoptical composition circuit 331 and an optical splitter circuit 332 areused. At this time, the optical composition circuit 331 and the opticalsplitter circuit 332 can be formed by combining many optical switches.

In the DNA chip of the invention, the DNA fragment is fixed onto thesubstrate. The substrate of the DNA chip of the invention ismanufactured using the structure in which the minute structures of theinvention are arranged on the substrate. At this time, the minutestructure has a large specific surface area, the detection efficiencybecomes high, and the size of the whole chip can be made small.

In the light emitting device of the invention, the first electrode, theluminescent layer, and the second electrode are sequentially depositedon the substrate in this order. The light emitting device of theinvention is manufactured using the structure including the area inwhich the minute structures of the invention are arranged periodically,or the structure in which the minute structures of the invention arearranged periodically on the substrate.

At this time, the first electrode, luminescent layer, and the secondelectrode may be deposited on either of the surface on which the minutestructures of the invention are not arranged and the surface on whichthe minute structures of the invention are arranged. According to theuneven structure containing the minute structures, the light extractionefficiency of the light emitting device is improved, and the luminousefficiency can be raised.

In the photoelectric transducer of the invention, the first electrode,the photoelectric conversion layer, and the second electrode aresequentially deposited on the substrate in this order. The substrate ofthe photoelectric transducer of the invention is manufactured using thestructure minute structure of the invention has the area arrangedperiodically, or the substrate is manufactured on the substrate usingthe structure with which the minute structure of the invention has thearea arranged periodically. A photoelectric transducer with highphotoelectric conversion efficiency is obtained by the uneven structurein which the photoelectric transducer contains the minute structures.

The optical lens of the invention is manufactured using the structurewhich includes the minute structure of the invention, or the structurein which the minute structures of the invention are arranged on thesubstrate. Thereby, a reliable minute optical lens is obtained.

Embodiment 1

FIG. 1A and FIG. 1B show the composition of an information recordingmedium 100A of the embodiment 1 of the invention. FIG. 1A is across-sectional view of the information recording medium and FIG. 1B isa top view of the information recording medium.

In the information recording medium 100A, a 50 nm-thick dielectric layer102 of ZnS—SiO2 (the molar ratio: 8:2), a 10 nm-thick light absorptionlayer 103 of AgInSbTe, and minute structures 104 are formed on a siliconsubstrate 101 with a thickness of 1 mm and a size of 10 cm by 10 cm.

The minute structures 104 are arranged as shown in FIG. 1B, andinformation is determined by the existence of minute structure 104.Specifically, when the recording medium 100A is irradiated by a laserbeam, a fluorescent light is emitted by the minute structure 104, and nofluorescent is emitted from the area 105 where no minute structure 104is arranged, so that this recording medium 100A may function as aninformation recording medium.

Each minute structure 104 is in a hemispherical configuration, thediameter of its bottom is about 150 nm, and the height is about 30 nm.The minute structures 104 are arranged with the period of 200 nm (markpitch), i.e., arranged at intervals of 50 nm.

Each minute structure 104 contains ZnS, SiO2 and CdTe (the molar ratio:77:20:3), and shows the behavior which is similar to that of fluorescentquantum dots. Information is read from the recording medium by scanninga fluorescence detection optical head in the direction indicated by thearrow in FIG. 1B. In the fluorescence detection optical head, theemitted fluorescent light is focused by a lens and passes through anoptical fiber and an optical filter, so that the fluorescence isdetected by amplifying it using a photomultiplier tube. Through theoptical head, the optical filter and the processing method of a lightsignal, detection of the fluorescence is possible even if it is weak.

FIG. 2A through FIG. 2D show the method of manufacturing the informationrecording medium 100A.

First, a dielectric layer 102, a light absorption layer 103, and a mixedmaterial layer 106 are deposited in this order on a silicon substrate101 by using a sputtering apparatus CFS-8EP-55 (from ShibauraMechatronics Co.) (refer to FIG. 2A). The mixed material layer 106includes ZnS, SiO2 and CdTe (the molar ratio: 77:20:3) and the thicknessis 160 nm.

Next, vacuum attraction of the obtained silicon substrate 101 to the XYstage is performed and the pulsed irradiation of the silicon substrate101 by a laser beam 107 with the wavelength of 405 nm from asemiconductor laser is carried out in a period of 200 nm through anobjective lens 108 with the NA of 0.85 (refer to FIG. 2B). The portionsof the substrate which are irradiated by the laser beam 107 at this timeare predetermined by the program. And etching is performed for 10seconds using a hydrofluoric acid 109 of 2% by weight (refer to FIG.2C). Then, it is observed using the scanning electron microscope thatthe minute structures 104 are formed at the irradiation portions by thelaser beam 107 (refer to FIG. 2D). It appears that the etchingresistance to hydrofluoric acid of the mixed material layer 106 improvesdue to a kind of sintering effect and the irradiation portions by thelaser beam 107 remain non-etched and a hemispherical pattern is left.

Accordingly, the minute structures 104 can be easily produced by usingheat lithography. Since the percentage of content of CdTe in the mixedmaterial layer 106 is 3% by weight, the information recording medium100A using fluorescence detection can be produced without affecting theproduction of minute structure 104. Since the recorded areas and thenon-recorded areas are discriminated by the existence of minutestructure 104, the obtained information recording medium 100A can beused as a ROM (Read Only Memory). Since the mixed material layer 106contains ZnS and SiO2, a change of the etching resistance can be usedand the refractive index can be adjusted.

Embodiment 2

FIG. 3A and FIG. 3B show the composition of an information recordingmedium 100B of the embodiment 2 of the invention. FIG. 3A is across-sectional view of the information recording medium and FIG. 3B isa top view of the information recording medium.

In the information recording medium 100B, a 50 nm-thick dielectric layer102 of ZnS—SiO2 (the molar ratio: 8:2), a 10 nm-thick light absorptionlayer 103 of Ge (germanium), a 20 nm-thick ZnS layer 111, and minutestructures 104 are formed on a polycarbonate substrate 110. Thepolycarbonate substrate 110 is a disc-like plate for optical disk with adiameter of 12 cm and a height of 20 nm, and it has lands and grooves ina period of 440 nm (track pitch).

The minute structures 104 are arranged as shown in FIG. 3B, andinformation is determined by the existence of minute structure 104.Specifically, when the recording medium 100B is irradiated by a laserbeam, a fluorescent light is emitted from the minute structure 104, andno fluorescent light is emitted from the area where no minute structure104 is arranged.

Each minute structure 104 is in a hemispherical configuration, thediameter of its bottom is about 150 nm, and the height is in a range of30-160 nm. The minute structures 104 are arranged with the period of 400nm (mark pitch).

Each minute structure 104 includes ZnS, SiO2 and CdTe (the molar ratio:77:20:3), and shows the behavior which is similar to that of fluorescentquantum dots. Information is read from the recording medium by scanninga fluorescence detection optical head in the direction indicated by thearrow in FIG. 3B. In the fluorescence detection optical head, theemitted fluorescent light is focused by a lens and passes through anoptical fiber and an optical filter, so that the fluorescence isdetected by amplifying it with a photomultiplier tube. Through theoptical head, the optical filter, and the processing method of a lightsignal, detection of the fluorescence is possible even if it is weak.

Next, the method of manufacturing the information recording medium 100Bwill be explained.

First, a dielectric layer 102, a light absorption layer 103, a ZnS layer111, and a mixed material layer are deposited in this order on apolycarbonate substrate 110 by using a sputtering apparatus CFS-8EP-55(from Shibaura Mechatronics Co.). The mixed material layer includes ZnS,SiO2 and CdTe (the molar ratio: 77:20:3), and the thickness is about 160nm.

Next, while the obtained polycarbonate substrate 110 is rotated at thelinear velocity of 4.5 m/second, focusing and tracking is performedusing the surface record type disc tester LM330 (from Shibasoku Co.).The pulsed irradiation of the polycarbonate substrate 110 by a laserbeam with the wavelength of 405 nm is performed in a period of 400 nmthrough an objective lens with the NA of 0.85 (5.0 mW pulsed lightoutput). The portions of the substrate irradiated by the laser beam arepredetermined by the program. And etching is performed for 10 secondsusing a hydrofluoric acid of 2% by weight. Then, it is observed usingthe scanning electron microscope that the minute structures 104 areformed at the irradiation portions by the laser beam. It appears thatthe etching resistance to hydrofluoric acid of the mixed material layerimproves due to a kind of sintering effect and the irradiation portionsby the laser beam remain non-etched and a hemispherical pattern isformed.

Accordingly, the minute structures 104 can be easily produced by usingheat lithography. Since the percentage of content of CdTe in the mixedmaterial layer is 3% by weight, the information recording medium 100Busing fluorescence detection can be produced without affecting theproduction of the minute structures 104. Since the recorded areas andthe non-recorded areas are discriminated by the existence of minutestructure 104, the information recording medium 100B can be used as aROM (Read Only Memory). Since the mixed material layer contains ZnS andSiO2, a change of the etching resistance can be used and the refractiveindex can be adjusted.

Since the laser beam irradiation can be performed while performingfocusing and tracking when the substrate on which the lands and groovesfor optical disk are formed is used, the minute structures 104 can bespeedily produced with good accuracy.

Embodiment 3

The pulsed light output dependency of the minute structure wasinvestigated. The pulsed light output was varied in a range of 1.5-7 mW.The method of manufacturing the minute structure was the same as that ofthe embodiment 2. As the material of minute structure, ZnS—SiO2 (themolar ratio: 8:2) was used.

FIG. 4A through FIG. 9B show the scanning electron microscopephotographs of the produced minute structures. The observation isperformed using a field-emission scanning electron microscope FE-SEMS-4100 (from Hitachi Ltd.).

In FIG. 4A through FIG. 9B, both the SEM photographs taken from the topsurface direction and the SEM photographs taken from the slantingdirection are shown. As is apparent from these SEM photographs, theconfiguration of minute structure including the height and the width isvaried in accordance with a change of the pulsed light output.

In the embodiment 3, even when the minute structure is formed in any ofthe shown configurations, it can be used as an information recordingmedium.

FIG. 10 shows the relationship between the pulsed light output and themaximum diameter of the minute structure. As is apparent from FIG. 10,the maximum diameter of minute structure does not show the linearity tothe pulsed light output. The configuration of the minute structureformed on the polycarbonate substrate on which the unevenness is formedis mainly classified into the configurations of Stages I-IV according tothe value of the pulsed light output (refer to FIG. 11A-11D) as follows.

Stage I (3.5-5.2 mW pulsed-light output): the minute structure 104 is inan aspheric configuration but it is in a hemispherical configuration.The maximum diameter of the minute structure 104 increases in accordancewith the increase in the pulsed light output (refer to FIG. 11A).

Stage II (5.2-6.8 mW pulsed-light output): the minute structure 104includes cylinder structures 104 a and a hemispherical structure 104 bformed in the center of the upper cylinder structure 104 a. The cylinderstructures 104 a include two upper and lower cylinder structures. Thelower cylinder structure increases in size in accordance with theincrease in the pulsed light output (refer to FIG. 11B).

Stage III (6.8-8.0 mW pulsed light output): the minute structure 104includes cylinder structures 104 a and a hemispherical structure 104 bformed in the center of the upper cylinder structure 104 a. The cylinderstructures 104 a include two upper and lower cylinder structures. Theupper cylinder structure is larger in size than the lower cylinderstructure (refer to FIG. 11C).

Stage IV (over 8 mW pulsed light output): the minute structure 104 is ina cylindrical configuration (refer to FIG. 11D).

In Stage I as shown in FIG. 4A through FIG. 5B, the minute structure 104is in a hemispherical configuration (refer to FIG. 11A). In Stage II andStage III as shown in FIG. 6A through FIG. 9B, the minute structure 104includes the cylinder structures 104 a and the hemispherical structure104 b. In Stage II, the minute structure 104 has the maximum diameter atthe lower one of the cylinder structures 104 a (refer to FIG. 11B). Onthe other hand, in Stage III, the minute structure 104 has the maximumdiameter at the upper one of the cylinder structures 104 a (refer toFIG. 11C). In Stage IV, the minute structure 104 has an opening formedin the center thereof and it is in a cylindrical configuration (refer toFIG. 11D).

The reason why the etching resistance of the mixed material layerimproves by irradiation of a laser beam is not strictly clear. Itappears that the mixed material layer is optically almost transparentand the light absorption layer absorbs the laser beam and it is heated,so that the mixed material layer is closely packed due to the sinteringeffect.

The heat distribution by the light from the light absorption layer whichabsorbs the laser beam is Gaussian distribution. And when a flatsubstrate is used, the configuration of the minute structure isfundamentally hemispherical. However, in a case where a substrate foroptical disk having unevenness is used, the spatial heat distributionbecomes somewhat complicated in a three-dimensional manner, andtherefore the configuration of the minute structure is as shown inStages I-IV.

Heat mainly occurs at the center of free space, and etching resistanceof Stage I improves in the part used as the high temperature of themixed material layer. In Stage II, since the thickness of a mixedmaterial layer is limited, heat radiation stops becoming concentriccircle-like, and the part near a light absorption layer becomes hightemperature easily. In Stage III, some factors, like unevenness of apolycarbonate substrate and the upper part serves as an air spaceinfluence, and rather than the lower part, the upper part of a mixedmaterial layer has bad heat dissipation, and is conjectured to becomehigh temperature easily. In Stage IV, evaporation of the lightabsorption layer is considered to be a key factor, and an opening isformed in the center of the cylindrical minute structure.

Each of the minute structures of Stages I-IV is a structure suitable forany of an information recording medium, a photonic crystal, an opticalnonreflection film, an optical switch, an optical filter, a plasmoniccrystal, etc. Since the configuration and the refractive index of theminute structure affect the optical properties, it is necessary toadjust the size and the refractive index for each configuration.

In the embodiment 3, the minute structure is produced from therelationship of the observation resolution of the scanning electronmicroscope using ZnS—SiO2. In high-density information recording media,narrow-pitch tracks and reduction of recording marks are important, andthe minute structure of the embodiment 3 can be made into the size ofseveral tens of nanometers in diameter. If the pitch intervals of landsand grooves, the material of the light absorption layer, the thickness,and the composition ratio of ZnS and SiO2 are changed, the configurationand the pulsed light output characteristic of the minute structure arealso changed slightly. The minute structure can be produced even whenthe material other than ZnS—SiO2 is used or another substance is mixedwith ZnS—SiO2 or the composition ratio is changed.

The minute structure can be easily produced using heat lithography asmentioned above. When the mixed material layer contains ZnS and SiO2, anetching resistance change can be used, and also the refractive index canbe adjusted.

Since laser beam irradiation is performed while performing focusing andtracking when the substrate in which the lands and grooves for opticaldisk are formed is used, the minute structures can be speedily producedwith good accuracy.

Embodiment 4

FIG. 12A and FIG. 12B show the composition of an optical nonreflectionfilm 100C of the embodiment 4 of the invention. What is different fromthe embodiment 1 is that the mixed material layer used is formed ofZnS—ZnO—SiO2 (the molar ratio: 6:2:2), and others are the same as in theembodiment 1.

FIG. 12A is a cross-sectional view of the optical nonreflection film andFIG. 12B is a top view of the optical nonreflection film.

Since the minute structures 104 having the configuration of Stage II-IIIof FIG. 11 are arranged in a period of 200 nm, optical nonreflectionfilm 100C controlled the Fresnel reflection of the light of a specifiedwavelength region (350-600 nm), and showed the nonreflectioncharacteristics by the moth-eye structure.

The minute structure 104 is easily producible using heat lithography asmentioned above. When the mixed material layer contains ZnS and SiO2, achange of the etching resistance can be used, and also the refractiveindex can be adjusted.

Any of the configurations of Stages I-IV of FIG. 11 is applicable to theoptical nonreflection film regardless of the configuration of the minutestructure. However, according to a difference in the configuration ofthe minute structure, it is necessary to adjust the height of minutestructure, the refractive index, and the period suitably. Although therefractive index of the material affects it, an optical nonreflectionfilm can be formed using a reversal structure of the moth-eye structure.And multilayers may be formed with the optical nonreflection film.

Embodiment 5

The optical waveguide shown in FIG. 13 was produced in the same manneras in the embodiment 1 except that the mixed material layer formed ofZnS—ZnO—SiO2 (the molar ratio: 6:2:2) is used. FIG. 13A and FIG. 13B area cross-sectional view and a top view of the optical waveguide,respectively. In the area in which optical waveguide 100D reflectslight, the minute structures 104 having the configuration of StageII-III of FIG. 11 are arranged in a period of 300 nm, and minutestructure 104 is not arranged at the propagation portion of light.

Since this reflects the light of the specified wavelength region(400-600 nm) resulting from the average refractive index and periodicgap of a periodical structure by a photonic band gap, as shown in FIG.13B, light travels.

In the optical waveguide by a photonic crystal, in order to be dependenton the degree of incident angle, the wavelength of light to reflectneeds to adjust the degree of incident angle, and needs to enter thelight of the wavelength corresponding to a photonic band gap wavelengthband.

The minute structure is easily producible using heat lithography asmentioned above. When a mixed material layer contains ZnS and SiO2, anetching resistance change can be used, and also a refractive index canbe adjusted.

The optical waveguide using a photonic band gap is applicable to anoptical filter, an optical switch, laser, etc. Although do not reflectlight and it is penetrated in the wavelength band near the photonic bandgap, the optical property which exceeded the limits of resolution, suchas the collimating effect and the lens effect, with the unique characterof the photonic crystal is seen theoretically and in phenomenon. Sucheffect is also acquired using the minute structure of the invention.

The optical waveguide is not based on the configuration of the minutestructure, but the minute structures having the configurations of StagesI-IV of FIG. 11A-11D may be arranged. The difference in theconfiguration of the minute structure needs to adjust the height ofminute structure, a refractive index, and a period suitably.

Although the characteristics differ in the configuration of the minutestructure also in the reversal structure of the periodical structure ofminute structure, the photonic band effect is acquired. For this reason,as a photonic crystal, both the periodical structure of minute structureand its reversal structure can be used.

Embodiment 6

The optical filter shown in FIG. 14A-14B was produced in the same manneras in the embodiment 1 except that the mixed material layer formed ofZnS—SrS—SiO2 (the molar ratio: 7:1:2) was used and the quartz substrate112 of a size of 10 cm by 10 cm was used. FIG. 14A and FIG. 14B are across-sectional view and a top view of the optical filter, respectively.

The minute structure 104 in optical filter 100E is hemispherical, is 150nm in diameter at the bottom, and 30 nm in height, and is arranged in aperiod of 200 nm (mark pitch). For this reason, when a laser beam isirradiated, optical filter 100E reflects the light of a specifiedwavelength region (300-500 nm) as an effect of subwavelength structureaccording to the degree of incident angle.

If light with a wavelength of 405 nm is entered into the field in whichminute structure 104 is formed at this time, changing an angle, incidentlight will be reflected at an angle of specification.

The minute structure 104 is easily producible using heat lithography asmentioned above. When the mixed material layer contains ZnS, SrS, andSiO2, an etching resistance change can be used, and also a refractiveindex can be adjusted.

Not only subwavelength structure but the effect of a photonic crystal isproduced from the periodical structure of minute structure 104. Thisfunctions as the optical filter which reflects the light of a specifiedwavelength region, or an optical switch. The incident angle and thewavelength of catoptric light depend for subwavelength structure or thephotonic crystal of each other. When the optical filter and the opticalswitch use the same phenomenon and do not want to make the light of aspecific wavelength band penetrated completely, they are operated as anoptical filter. It becomes an optical switch to use as an opticalelement which controlled ON and OFF of the penetration of light.

In the embodiments 1 to 6, the material in particular used as a lightabsorption layer is not limited, but Si besides AgInSbTe and Ge, a groupIII-V semiconductor, a 4 Yuan mixed crystal compound, etc. arementioned. The method of applying heat other than the method ofirradiating a laser beam locally as heat lithography is also possible.However, it excels in respect of directivity and stability, and sincethe production accuracy of minute structure is high, it is preferred toglare a laser beam.

Embodiment 7

The master substrate shown in FIG. 15 was produced. The master substrate200A is an object with a capacity of 25 GB for BD-ROM (Blu-ray Disc-ReadOnly Memory), it has the area where pattern 201 a of the recording pitsarranged periodically, and a track pitch is 0.32 micrometer. Thematerial of the master substrate 200A is quartz, and can manufacture astamper and an optical information recording medium (such as movierecorded contents) according to an injection molding transferringprocess based on the master substrate 200A.

The method of manufacturing the master substrate 200A is shown in FIG.16A-16F. First, a mixed material layer 202 with a thickness of 40 nmwhich becomes flat disc-like quartz substrate 201 from ZnS, SiO2 andZnTe (the molar ratio: 70:20:10) was formed through RF sputtering usinga sputtering apparatus CFS-8EP (from Shibaura Mechatronics Co.) (referto FIG. 16A).

Next, the focus of the blue laser light 204 whose wavelength by which NAof laser beam irradiation equipment was focused with objective lens 203of 0.85 is 405 nm was carried out to the surface of mixed material layer202, and the predetermined area was irradiated with 5 mW pulsed lightoutput (refer to FIG. 16B). It enabled it to form a pattern using thestrategy which is formed of information on ROM at this time.

Then, it was immersed in a hydrofluoric acid 205 for 10 seconds 2% byweight (refer to FIG. 16C), and was made to dry. As a result, almosthemispherical minute structure 206 which is formed of ZnS, SiO2 and ZnTe(the molar ratio: 70:20:10) was formed on quartz substrate 201 (refer toFIG. 16D).

Then, it installed in RIE (Reactive Ion Etching) equipment, and etchingby CF4 gas was performed. As a result, quartz substrate 201 used minutestructure 206 as the mask, and was etched (refer to FIG. 16E).

Removal of the minute structure 206 formed pattern 201 a reflecting theconfiguration of the mask (refer to FIG. 16F).

The height of pattern 201 a which is formed of quartz was about 40 nm asa result of measurement by AFM (atomic force microscope). Althoughpoint-like pattern 201 a is formed, if continuous irradiation of theblue laser light 204 is carried out, a linear pattern (groove) is formedand a stamper for the object for R substrates (Recordable substrate) orRW substrates (Rewritable substrate) can also be produced.

On the other hand, it is uncertain whether the minute structure can beformed or not, and this depends on the composition ratio of ZnS, SiO2and ZnTe. When the evaluation about the relationship between thecomposition ratio and the propriety of pattern formation was carriedout, the result shown in Table 1 was obtained.

TABLE 1 Composition Ratio (mol %) Formation of ZnTe ZnS SiO₂ PatternSample 1 10 70 20 yes Sample 2 5 65 30 no Sample 3 10 50 30 no Sample 410 85 5 no Sample 5 15 68 17 yes Sample 6 32 60 8 no Sample 7 22 65 13yes

As is apparent from Table 1, the pattern was able to be formed in thecases of the samples 1, 5, and 7, and no pattern was able to be formedin the cases of the samples 2, 3, 4, and 6. In order to check therelationship between the composition ratio and the propriety of patternformation, evaluation of the samples 1-7 was carried out. When theetching resistance to hydrofluoric acid of each sample, before and afterthe irradiation of a blue laser light with the wavelength of 405 nmfocused by the objective lens with the NA of 0.85 was given at 1-8 mWpulsed light output, was evaluated, the result shown in Table 2 wasobtained.

TABLE 2 Etching Resistance Etching Resistance Before Irradiation AfterIrradiation Sample 1 no yes Sample 2 no no Sample 3 no no Sample 4 yesyes Sample 5 no yes Sample 6 yes yes Sample 7 no yes

As is apparent from Table 2, a pattern can be formed in a case in whichthe sample before the laser beam irradiation was applied had no etchingresistance and the sample after the laser beam irradiation was appliedhad some etching resistance. When the samples 1, 3, and 4 are reviewed,in order for the sample to have no etching resistance before the laserbeam irradiation, SiO2 is needed, and it is estimated that thepercentage of content of SiO2 needed is more than 10 mol %.

On the other hand, when it has a too large percentage of content of SiO2after the laser beam irradiation, as in the sample 3, there is noetching resistance. Since there are many components (ZnS and SiO2) whichpenetrate a laser beam like sample 2 when there are few rates of ZnTe,absorbing of a laser beam becomes inadequate. In order that ZnTe mayraise optical absorption ability, it is required, but if there are toomany rates like sample 7, the rate of ZnS will become inadequate andsystematization by generation of heat accompanying absorption of a laserbeam will not be promoted. The composition ratio of samples 1, 5, and 7in which the pattern is formed is also taken into consideration, and, asfor the rate of ZnS, the rate of more than 60 mol % and ZnTe is presumedless than 30 mol %.

Moreover, when Ag was used instead of ZnTe and the evaluation wascarried out similarly, the results shown in Table 3 and Table 4 wereobtained.

TABLE 3 Composition Ratio (mol %) Formation of Ag ZnS SiO₂ PatternSample 8 10 72 18 yes Sample 9 40 50 10 no Sample 10 40 40 20 no Sample11 15 80 5 no Sample 12 15 70 15 yes Sample 13 32 60 8 no Sample 14 1065 25 yes Sample 15 10 81 9 no Sample 16 10 80 10 yes Sample 17 9 81 10no Sample 18 10 50 30 yes Sample 19 10 49 31 no Sample 20 9 50 31 no

TABLE 4 Etching Resistance Etching Resistance Before Irradiation AfterIrradiation Sample 8 no yes Sample 9 yes yes Sample 10 no no Sample 11yes yes Sample 12 no yes Sample 13 yes yes Sample 14 no yes Sample 15yes yes Sample 16 no yes Sample 17 no no Sample 18 no yes Sample 19 nono Sample 20 no no

As is apparent from Table 3 and Table 4, in samples 8-14, even if Ag isused instead of ZnTe, it can be said that the relation between thecomposition ratio of ZnS, SiO2 and Ag and the propriety of patternformation is the same. On the other hand, in sample 16, the patternformation was possible, but the pattern of sample 8 was clearer. Patternformation was not completed in sample 15 and sample 17 although sample15 and sample 17 has near composition ratios as sample 16.

In sample 15, there is etching resistance before it is irradiated by thelaser beam as shown in Table 4, and pattern formation is impossible, andit is shown that the ratio of SiO2 of 9 mol % is inadequate. On theother hand, in sample 17, there is no etching resistance before it isirradiated by the laser beam, but the percentage of Ag is 9 mol %, andit is conceivable that the dose of laser beam is inadequate and apattern was not able to be formed. It is conceivable that in this case,a pattern can be formed if it is irradiated by a higher output laserbeam.

Since the calorific value accompanying absorption of the laser beam willchange if the material added as material C is changed, the irradiationconditions (pulsed light output, pulse width) of the laser beam requiredfor pattern formation are also changed. The same thing can be said aboutmaterial A′. The ratio of SiO2 at which pattern formation is possible ismore than 10 mol % when etching using a hydrofluoric acid is performed,and the same thing can be said for in the case where SiO is contained.As is apparent from samples 18-20, the ratio of SiO2 at which patternformation is possible is less than 30 mol %. In sample 18, thepercentage of content of SiO2 is 30 mol %, a pattern is formed, but thepattern is not clear. In samples 19 and 20, the percentage of content ofSiO2 is 31 mol %, and the minute structure does not remain mostly.

Even if the pulsed light output of the laser beam is increased, theratio of material C is decreased and the ratio of material A′ isincreased, the ratio of SiO2 at which pattern formation is possible isless than 30 mol %. In order to form a clear pattern, it is preferredthat SiO2 is moderately contained in a range of 10-30 mol %.

When forming a mixed material layer by the sputtering method, onesputtering target which is formed of mixed materials may be used, or asputtering target may be prepared for each material and co-sputteringmay be performed. There are the case where an oxygen deficiency in SiO2arises and SiOx (x=1−2) is produced, and the case where the surfaceroughness of the mixed material layer differs, according to the methodof sputtering, but the quality of the film of the mixed material layerdoes not change greatly.

It is conceivable that when the mixed material layer is irradiated by alaser beam and the materials are mixed within the mixed material layer.

The extinction coefficient k of ZnS—SiO2 (the molar ratio: 80:20) to theblue laser whose wavelength is 405 nm is about 1×10⁻³. On the otherhand, the extinction coefficient k of the mixed material layer of thesample 5 is about 1×10⁻¹.

Thus, the blue laser absorption ability can be raised by adding ZnTe tothe mixed material layer. Since the calorific value in the mixedmaterial layer is based on the pulsed light output of the laser beam,when it is irradiated by the commercial red or blue semiconductor laserbeam, the extinction coefficient k of about 1×10⁻¹ is enough for themixed material layer.

Although the transmittance in the visible light region of 40 nm-thickZnS—SiO2 (the molar ratios: 50:50-90:10) is about 100%, if ZnTe or Ag isadded, the transmittance falls and its optical absorption abilityimproves as the ratio of ZnTe or Ag increases. However, the compositionof the mixed material layer is important for production of minutestructure ZnS more than 60 mol % and SiO2 10-30 mol % and ZnTe, or Agless than 30 mol % containing is preferred.

Unless it fulfills such conditions, the almost hemispherical minutestructure which has a smooth end by etching may not be formed. Since thepercentage of content of SiO2 in the mixed material layer is 10% byweight or more, it etches in a hydrofluoric acid, but almosthemispherical minute structure remains because irradiation of the laserbeam is received and the etching resistance to hydrofluoric acid isimproved. Since the same element as ZnS is included as material C whenZnTe is used, as compared with the case where Ag is used, the end ofminute structure becomes still smoother.

In the embodiment 7, since minute structure 206 is almost hemispherical,master substrate 200A can be manufactured. If the pulsed light output ofblue laser light 204 shall be 7 mW instead of minute structure 206 shownin FIG. 16D, as shown in FIG. 17, minute structure 207 of the form bywhich hemispherical structure is formed on a generally cylinderstructure will be formed.

In order to etch into quartz substrate 201 finally, the configuration ofthe minute structure affects the pattern shape of recording pits. Atthis time, there is the feature that the direction which uses minutestructure 207 as a mask and etches it is etched almost perpendicularlyas compared with the case where minute structure 206 is used.

Embodiment 8

The optical nonreflection film shown in FIG. 18 was produced. FIG. 18Aand FIG. 18B are a cross-sectional view and a top view of the opticalnonreflection film, respectively. The optical nonreflection film 200B ismade of quartz and includes cylindrical patterns 201 b each with adiameter of about 150 nm and a height of about 250 nm arranged in aperiod of 200 nm.

As compared with quartz substrate 201 of the same thickness, opticalnonreflection film 200B raises the transmittance to the light whosewavelength is in a range of 400-600 nm, and is close brought to 100%.This is for periodical structure's turning into the moth-eye structure,controlling reflection, and making light penetrate.

The method of manufacturing the optical nonreflection film 200B is thesame as that of the embodiment 7 except that it is irradiated by theblue laser light 204 in a period of 200 nm. After producing with awafer, dicing divides optical nonreflection film 200B into severalmillimeter angle, and it is obtained by washing in order to removeimpurities.

As shown in FIG. 16D, the minute structure 206 was formed on quartzsubstrate 201 as an optical nonreflection film. Since the material ofminute structure 206 differs from quartz, the effect as an opticalnonreflection film may fade, or exfoliation may arise at a dicingprocess and the yield may become low. From this, a pattern may betransferred and reproduced, after etching to quartz substrate 201 ifneeded. At this time, the configuration of the pattern formed in thesurface of quartz substrate 201 turns into form near minute structure206 which serves as a mask fundamentally.

However, since the etching rate to CF4 of minute structure 206 is smallenough, an aspect ratio can also produce high-shaped pattern 201 b. Whenreproducing, a pattern can be transferred into the material which makesresin the main ingredients using nano imprint technology, such as a heatnano imprint, an optical nano imprint, and soft lithography.

Embodiment 9

The optical nonreflection film shown in FIG. 19A-19B was produced. FIG.19A and FIG. 19B are a cross-sectional view and a top view of theoptical nonreflection film, respectively. In the optical nonreflectionfilm 200C, the minute structures 208 are arranged in a period of 400 nmon the quartz substrate 201. The materials of minute structure 208 areZnS, SiO2 and ZnTe—ZnO (the molar ratio: 64:18:10:8). The minutestructures 208 are mostly in a cylindrical configuration, the outerdiameter is about 300 nm and the inside diameter is about 90 nm, and theheight is about 50 nm.

As compared with the quartz substrate of the same thickness, the opticalnonreflection film 200C raises the transmittance to the light whosewavelength is in a range of 400-600 nm, and is close brought to 100%.This is for the periodical structure by minute structure 208 turninginto the moth-eye structure, controlling reflection, and making lightpenetrate.

The method of manufacturing the optical nonreflection film 200C is thesame as that of the embodiment 7 (with FIG. 16E-16F ignored) except thatit is irradiated by the blue laser light 204 with the pulsed lightoutput of 9 mW in a period of 400 nm. Since ZnS, SiO2, ZnTe and ZnO (themolar ratio: 64:18:10:8) have high transmittance, it needs to enlargethe pulsed light output of blue laser light 204. If the pulsed lightoutput of blue laser light 204 is changed to 8 mW, as shown in FIG. 20,the minute structure 209 in a cylindrical configuration with the hollowpart and the enlarged bottom will be formed.

Embodiment 10

The information recording medium shown in FIG. 21 was produced. Theminute structures 211 are arranged in a period of 160 nm on thedisc-like polycarbonate substrate 210 with a diameter of 12 cm, and theinformation recording medium 200D has repetition unevenness of lands andgrooves. Each minute structure 211 has a diameter of about 90 nm at thebottom and a height of about 30 nm, and is in an almost hemisphericalconfiguration. In the information recording medium 200D, information isdetermined by the existence of minute structure 211.

When the information recording medium 200D is irradiated by a laserbeam, the minute structure 211 emits fluorescent light, and nofluorescent light is emitted from the area where no minute structure 211is arranged. For this reason, when a fluorescence detection optical headis scanned, information can be read out from the recording mediumaccording to the detection of fluorescence.

The materials of minute structure 211 are ZnS, SiO2 and CdTe (the molarratio: 77:20:3), and the minute structure 211 has the same effect asfluorescent quantum dots. When reading information, the emittedfluorescent light is focused by using the lens of the optical head, andfluorescence is detected by amplifying it with a photomultiplier tubevia an optical fiber and an optical filter. Thereby, it can be detectedeven when the fluorescent light is weak.

The method of manufacturing the information recording medium 200D is thesame as that of the embodiment 7 (with FIG. 16E-16F being ignored)except that it is irradiated by the blue laser light 204 with the pulsedlight output 8 mW. Although it is produced on the disc-likepolycarbonate substrate 210 in the embodiment 10, it may be produced ona rectangular substrate using an XY stage. In this case, vacuumattraction to the XY stage is performed, and pulsed irradiation of thelaser beam is performed.

Embodiment 11

The optical waveguide shown in FIG. 22A and FIG. 22B was produced. FIG.22A and FIG. 22B are a cross-sectional view and a top view of theoptical waveguide, respectively. The optical waveguide 200E has theperiodic area where the minute structures 213 are arranged in a periodof 400 nm on the silicon substrate 212, and the light with thewavelength of 780 nm is reflected by the photonic band gap caused by theaverage refractive index of the periodic area, and the gap of the minutestructures 213. No minute structure 213 is formed in the portion wherethe light travels.

In the hemispherical structure formed on the cylinder structure, thediameter of its bottom is about 200 nm, and the height is about 50 nm.The materials of the minute structure 213 are ZnS, SiO2 and ZnO (themolar ratio: 65:20:15).

The method of manufacturing the optical waveguide 200E is the same asthat of the embodiment 7 (with FIG. 16E-16F being ignored) except thatit is irradiated by the blue laser light 206 with the pulsed lightoutput 7 mW.

The photonic crystal using a photonic band gap is applicable to opticalelements other than optical waveguide, such as an optical filter and anoptical switch. Although do not reflect light and it is penetrated inthe wavelength band near the photonic band gap, the optical propertybeyond the limits of resolution, such as the collimating effect and thelens effect, is seen theoretically and in phenomenalism with the uniquecharacter of the photonic crystal. Such effect is also acquired by theoptical element of quartz substrate.

Embodiment 12

The optical filter shown in FIG. 23 was produced. The optical filter200F uses subwavelength structure, and the minute structures 214 arearranged in a period of 300 nm on the quartz substrate 201.

In the hemispherical structure formed on the cylinder structure, thediameter of its bottom is about 200 nm, and the height is about 50 nm.The materials of the minute structure 214 are ZnS, SiO2 and Au (themolar ratio: 72:18:10).

The method of manufacturing the optical filter 200F is the same as thatof the embodiment 7 (with FIG. 16E-16F being ignored) except that it isirradiated by the blue laser light 204 with the pulsed light output 8mW.

Alternatively, as shown in FIG. 24, an optical filter 200G of quartz maybe formed through the process of FIG. 16E-16F. The optical filter 200Ghas the patterns 201 c arranged in a period that is the same as that ofthe optical filter 200F.

When they are irradiated by a laser beam, the optical filters 200F and200G reflect the light with a specified wavelength due to the photonicband gap, and the filters function as an optical switch. For example, ifthe light with the wavelength of 405 nm is incident to the opticalfilters 200F and 200G while the incidence angle is changed, the light isreflected at a specific incidence angle.

Even if the section formed periodically the linear minute structurewhich is a rectangle mostly by carrying out continuous irradiation ofthe blue laser light 204 instead of minute structure 214, the effect asan optical switch was acquired. When linear minute structure was formed,the effect as an optical switch was mutually acquired also as astructure of the shape of perpendicular meshes of a net. LER was alsosmaller than the value of the resist in photo lithography, and was setto 1 nm or less.

The optical filter functions according to subwavelength structure andthe photonic band gap effect as the optical filter which reflects thelight of a specified wavelength, or an optical switch. The incidentangle and the wavelength of catoptric light depend for subwavelengthstructure or the photonic crystal of each other. The same phenomenon isused and an optical filter and an optical switch function as an opticalfilter to penetrate the light of a specified wavelength completely. Itbecomes an optical switch to use as an optical element which controlledON and OFF of the penetration of light.

Embodiment 13

FIG. 25A through FIG. 25D show the scanning electron microscopephotographs of the minute structure of the embodiment 13. The minutestructure is formed on the polycarbonate substrate in which a trackpitch has a land groove which is 400 nm (line width of 200 nm, racewaygroove width of 200 nm), and the materials are ZnS, SiO2 and Ag (themolar ratio: 72:18:10).

The method of manufacturing the minute structure is the same as that ofthe embodiment 7 except having changed the pulsed light output of bluelaser light 204 using the sputtering target which is formed of ZnS, SiO2and Ag (the molar ratio: 72:18:10).

The pulsed light outputs of FIG. 25A, FIG. 25B, FIG. 25C, and FIG. 25Dare 6.5 mW, 7.0 mW, 8.0 mW, and 9.0 mW, respectively. The minutestructure in FIG. 25A or FIG. 25B is in a hemispherical configuration,the minute structure in FIG. 25C is in a configuration in which ahemispherical structure is formed on the cylinder structure, and theminute structure in FIG. 25D is in a cylindrical configuration. Theconfiguration of the minute structure can be evaluated by using atransmission electron microscope or an atomic force microscope, otherthan a scanning electron microscope.

FIG. 26 shows the relationship between the pulsed light output and theouter diameter or the inside diameter of the minute structure. As shownin FIG. 26, the pulsed light output increases as the outer diameter ofthe minute structure increases, and a hollow portion (opening) arises inthe center of the minute structure at 9 mW. The size of the minutestructure may be changed with the pulse width at the time of laser beamirradiation (irradiation time). The pulse width in this case is in arange of 10 to 15 nanoseconds. Although the size of the minute structureto the pulsed light output is changed in accordance with the compositionratio, materials, etc., the same pulsed light output dependency can beseen also when materials other than Ag are used.

FIG. 27A and FIG. 27B show the scanning electron microscope photographsof another example of the minute structure of the embodiment 13. Thisminute structure is formed on the polycarbonate substrate in which thetrack pitch of lands and grooves is 400 nm (the line width: 200 nm, thegroove width: 200 nm) and the materials used are ZnS, SiO2 and ZnTe (themolar ratio: 68:17:15).

The method of manufacturing the minute structure is the same as that ofthe embodiment 7 except that the pulsed light output of blue laser light204 is changed and the two sputtering targets of ZnTe and ZnS—SiO2 (themolar ratio: 80:20) are used. The composition of the film formed by thesputtering method was checked by the element analysis. The pulsed lightoutput of FIG. 27A was 6.0 mW and the pulsed light output of FIG. 27Bwas 7.0 mW.

FIG. 28 shows the scanning electron microscope photograph of anotherexample of the minute structure of the embodiment 13. This minutestructure is formed on the polycarbonate substrate in which the trackpitch of lands and grooves is 400 nm (the line width: 200 nm, the groovewidth: 200 nm), and the materials-used are ZnS, SiO2 and Au (the molarratio: 72:18:10).

The method of manufacturing the minute structure is the same as that ofthe embodiment 7 except that the pulsed light output of blue laser light204 was 3.0 mW and the two sputtering targets of Au and ZnS—SiO2 (themolar ratio: 80:20) was used.

When the minute structures of FIG. 25A-25D, FIG. 27A-27B, and FIG. 28are compared, it turns out that the end of the minute structure of FIG.27A-27B is the smoothest. When the linear minute structures wereproduced by using the same materials as the minute structures of FIG.25A-25D, FIG. 27A-27B, and FIG. 28 and carrying out continuousirradiation of the laser beam and the respective LER were compared, thecase where the same materials as the minute structure of FIG. 27 wereused was the smallest. This is because Zn is contained in the materialA′ and the material C as the common element.

The minute structures were able to be produced in the cases where any ofAl, Cu, Pt, Sb, Te, Ge, Si, Bi, Mn, W, Co, Nb and these alloys, forexample, InSb, AgInSbTe, GeSbTe, etc. is used as the material C.Similarly, the minute structures were able to be produced in the caseswhere any of ZnMgTe, CsZnTe, ZnMgSSe, SbZn, ZnCrO4, ZnZrO3, ZnWO4,ZnTiO3, Zn3N2, ZnF2, ZnSnO3, ZnMoO4, GeS2, CoS, SnS, etc. is used. In acase where a material with a relatively large transmittance to bluelaser beam, like ZnO, is used as the material Cr, if the materials usedare ZnS, SiO2, ZnTe and ZnO (64:18:10:8), the minute structure with asmooth end was able to be produced. Also when any of ZnSe, MnS, and SrSis used as the material C, the minute structure with a smooth end wasable to be produced.

Embodiment 14

The optical nonreflection film 200B shown in FIG. 18A and FIG. 18B wasproduced. The optical nonreflection film 200B is formed of quartz, andcylindrical patterns 201 b with a diameter of about 150 nm and a heightof about 250 nm are arranged in a period of 200 nm. When compared withthe quartz substrate of the same thickness, the optical nonreflectionfilm 200B increases the transmittance to the light whose wavelength isin a range of 400-600 nm, and the increased transmittance is nearly100%. This is because the periodical structure turns into the moth-eyestructure, avoiding reflection and allowing light penetration.

The method of manufacturing the optical nonreflection film 200B is thesame as that of the embodiment 7 except that the irradiation of bluelaser light 204 is performed in a period of 200 nm, the mixed materiallayer 202 of FeS—SiO2 (the molar ratio: 80:20) is formed and the twosputtering targets of FeS and SiO2 are used. After the opticalnonreflection film 200B is formed using a wafer, it is divided intopieces of several millimeters by dicing of the wafer, and the opticalnonreflection film 200B is obtained by washing to remove impurities.

ZnS, CaS, and SrS are almost transparent in a visible light region andhave a small optical absorption ability. In contrast, FeS has acomparatively large optical absorption ability among these sulfurcompounds. FeS—SiO2 (the molar ratio: 80:20) absorbs a laser beam withan emission wavelength in a visible light region. For this reason, FeSfunctions as a material for raising the optical absorption ability.

As shown in FIG. 16D, an optical nonreflection film in which the minutestructures 206 are formed on the quartz substrate 201 can be also used.Since the material of the minute structures 206 differs from quartz,there may be a case in which the optical nonreflection film effect isweak or exfoliation arises at the time of dicing process and the yieldbecomes low. To avoid this, pattern transferring may be performed afteretching is performed to the surface of the quartz substrate 201 ifneeded. At this time, the configuration of the pattern formed on thesurface of the quartz substrate 201 is fundamentally similar to that ofthe minute structure 206 used as a mask. However, since the etching rateto CF4 of the minute structure 206 is small enough, a pattern in theconfiguration with a high aspect ratio can be formed.

When reproducing is performed, the pattern may be transferred into thematerial containing a resin as the main ingredient, by usingnanoimprinting technology, such as thermal nanoimprinting, opticalnanoimprinting, or soft lithography.

Embodiment 15

FIG. 29A through FIG. 29D show the scanning electron microscopephotographs of the minute structure of the embodiment 15. Such minutestructure is formed on the polycarbonate substrate in which the trackpitch of lands and grooves is 400 nm (the line width: 200 nm, the groovewidth: 200 nm) and the material used is FeS—SiO2 (the molar ratio:80:20). The method of manufacturing the minute structure is the same asthat of the embodiment 7 except that the mixed material layer 202 ofFeS—SiO2 (the molar ratio: 80:20) is formed, the two sputtering targetsof FeS and SiO2 are used, and the pulsed light output of blue laserlight 204 is charged. The pulsed light outputs of FIG. 29A, FIG. 29B,FIG. 29C, and FIG. 29D are 1.5 mW, 2.0 mW, 3.0 mW, and 4.5 mW,respectively.

The minute structure in FIG. 29A is in a hemispherical configuration,the minute structure in FIG. 29B or FIG. 29C is in a configuration inwhich a hemispherical structure is formed on a cylinder structure, andthe minute structure in FIG. 29D is in a cylindrical configuration. Thesize of minute structure varies depending on the pulse width or thepulsed light output of the laser beam.

FIG. 30A and FIG. 30B show the scanning electron microscope photographsof another example of the minute structure of the embodiment 15. Suchminute structure is formed on the polycarbonate substrate in which thetrack pitch of lands and grooves is 400 nm (the line width: 200 nm, thegroove width: 200 nm), and the material used is FeS—SiO2 (the molarratio: 76:24).

The method of manufacturing the minute structure is the same as that ofthe embodiment 7 except that the mixed material layer 202 of FeS—SiO2(the molar ratio: 76:24) is formed, the two sputtering targets of FeSand SiO2 are used, and the pulsed light output of blue laser light 204is changed. The pulsed light output of FIG. 30A and FIG. 30B are 1.1 mWand 1.4 mW, respectively.

The minute structure 206 is formed through the irradiation of blue laserlight 204, the immersion in a hydrofluoric acid 205 and the etching. Inthe area irradiated by blue laser light 204, FeS and SiO2 may besystematized and the etching resistance to hydrofluoric acid 205 mayimprove.

Embodiment 16

The minute structure 208 which is constructed as shown in FIG. 19 isformed on the quartz substrate 201. The materials of the minutestructure 208 are ZnS, SiO2 and Au (the molar ratio: 72:18:10). At thistime, a slide glass may be used instead of the quartz substrate 201.

The method of manufacturing the minute structure 208 is the same as thatof the embodiment 9 except that the pulsed light output is 8 mW. Next, aDNA chip is produced as follows. By using an ink jet system, 10,000 ormore kinds of DNA fragments are arrayed and fixed as minute spots on thequartz substrate 201 on which the minute structure 208 was formed. Theink jet method is advantageous for controlling of the discharge amountfrom an ejection hole.

The DNA chip is made to react (hybridization) with the sample DNA inwhich labeling of the discovery gene of the cell is performed withfluorescent coloring matters Cy3 (green) and Cy5 (red). As a result ofthe reaction of mutually complementary DNAs, the minute spots havingcorresponding DNAs are colored. The color of such minute spots is readout using a high-resolution DNA chip analysis device, and the functiondata of the sample DNA is obtained from DNA on the DNA chip.

Volume production of DNA chips is possible as follows. A flat, disc-likequartz substrate 201 as in the embodiment 7 is rotated, the DNS chipsare formed on a wafer with a large area, and the wafer is cut into DNAchips by dicing. For example, the DNA chips with a size of about 4 mmsquares can be produced with low cost. DNA chips may be produced usingan XY stage.

In order to raise the detection efficiency of DNA, it is important howthe DNA fragments be arrayed and fixed as the minute spots. The minutestructure in the embodiment 16 is arranged with a large specific surfacearea. At this time, the DNA chip of the embodiment 16 can bemanufactured with low cost when compared with the DNA chip manufacturedusing photolithography, etc. The minute structure in a cylindricalconfiguration as shown in FIG. 19A-19B is present uniquely to heatlithography, and its specific surface area is comparatively large.

DNA chips may be manufactured using materials and manufacturing methodsother than the embodiment 16. At this time, a certain oxygen deficiencymay arise in SiO2. A material for raising the optical absorptionability, such as a metal or an alloy, may be used as the material C.When a fluorescent material, such as CdTe or CdSe, is selected as thematerial C, fluorescence detection may be used. When a metal, such asAu, is used as the material C, the plasmon effect is expectable.

Embodiment 17

FIG. 32 shows the composition of a polarization separator element 300 ofthe embodiment 17. The polarization separator element 300 includes a ZnSlayer 302 which is formed on a polycarbonate substrate 301, and linearminute structures 303 which are periodically arranged on the ZnS layer302. The polarization separator element 300 has the function to separatea light 310, having a wavelength specified according to thecharacteristics (a period, a refractive index) of the polarizationseparator element 300, into P polarized light 311 and S polarized light312. The light of P polarized wave is a polarization component in whichthe plane of vibration of the electric field vector is parallel to aplane of incidence, and the light of S polarized wave is a polarizationcomponent in which the plane of vibration of the electric field vectoris perpendicular to a plane of incidence.

FIG. 33A through FIG. 33D are diagrams for explaining the method ofmanufacturing the polarization separator element 300 of the embodiment17. First, a 0.6 mm thick polycarbonate substrate 301 in which theunevenness (lands and grooves) with a height of 20 nm and a pitch of 200nm is formed in the shape of a concentric circle is produced through theknown optical disc manufacturing process using a master substrate and astamper and injection molding. Next, a 10 nm thick ZnS layer 302, and a200 nm thick mixed material layer 304 of ZnS, SiO2 and Zn (the molarratio: 64:13:33) are deposited on the polycarbonate substrate 301 inthis order through RF sputtering using a sputtering apparatus CFS-8EP-55(from Shibaura Mechatronics Co.) (refer to FIG. 33A).

A blue laser light 306 with a wavelength of 405 nm from a laser beamirradiation apparatus (from Shibasoku Co.) which is condensed by anobjective lens 305 with NA of 0.85 is focused on the surface of themixed material layer 304 in which tracking is carried out. The laserlight is continuously applied at 3.5 mW optical output to thepolycarbonate substrate 301 which is rotated (refer to FIG. 33B).

Then, the polycarbonate substrate 301 is immersed in a hydrofluoric acid307 of 2% by weight for 10 seconds and etching is performed (refer toFIG. 33C). After rinsing it with pure water and drying it up, thepolarization separator element 300 in which the minute structures 303are arranged periodically is obtained (refer to FIG. 33D).

The mixed material layer 304 adequately irradiated by the laser beam 306remains non-etched and it turns into the minute structure 303. In theembodiment 17, a part of the mixed material layer 304 formed as the land(convex) remains, and a part of the mixed material layer 304 formed asthe groove (concave) is removed. For this reason, adjoining minutestructures 303 are interconnected.

FIG. 34A and FIG. 34B show the scanning electron microscope photographsof the polarization separator element 300 of the embodiment 17. FIG. 34Ais a top view of the polarization separator element and FIG. 34B is aperspective view of the polarization separator element when across-section of the polarization separator element 300 is formed usinga focused ion beam (FIB). In order to form a cross-section, a carbonprotection layer 308 is deposited on the upper part of the minutestructure 303 in FIG. 34B.

As is apparent from FIG. 34A-34B, the linear minute structures 303 arearranged periodically in the polarization separator element 300. Thepolarization separator element in which the linear patterns are formedin this way is called a wire grid polarizer.

By entering S polarized light into the polarization separator element300 (see FIG. 33A) in which the polycarbonate substrate 301, the ZnSlayer 302, and the mixed material layer 304 are formed, the wavelengthdependency of the transmittance to S polarized light was measured asshown in FIG. 35. Similarly, by entering S polarized light into thepolarization separator element 300 which is rotated by 90 degrees, andusing a high-speed spectroscopic ellipsometer M-2000DI (from J. A.Woollam Japan) as a measuring device, the measurement spot diameter isabout 3 mm and the measurement is done in the mode of transmittancemeasurement using linear polarization.

At this time, the polarization separator element 300 is larger in sizethan the measurement spot diameter.

As is apparent from FIG. 35, the center wavelength in the case of thepolarization separator element 300 which is not rotated by 90 degrees isabout 747 nm and dip is seen. In the case of the polarization separatorelement 300 which is rotated by 90 degrees, dip is not seen. Therefore,the polarization separator element 300 has a polarization separationfunction in a wavelength zone of 650-840 nm around the center wavelengthof about 747 nm.

Next, a polarization separator element 300 is produced in the samemanner as the above example except that the continuous optical output oflaser beam 304 is changed to 3.0 mW and 2.5 mW.

FIG. 36A and FIG. 36B show the scanning electron microscope photographsof the polarization separator element 300 when the continuous opticaloutput is set to 2.5 mW. FIG. 36A is a top view of the polarizationseparator element and FIG. 36B is a perspective view of the polarizationseparator element when a cross-section of the polarization separatorelement 300 is formed using a focused ion beam (FIB). In order to form across-section, a carbon 308 is deposited on the upper part of the minutestructure 303 in FIG. 36B.

FIG. 37 shows the wavelength dependency of the transmittance to Spolarized light of the polarization separator element 300. As isapparent from FIG. 37, in the case of the polarization separator element300 which is rotated by 90 degrees and the continuous optical output isset to 2.5 mW, dip is not seen similar to the above example. In the caseof the polarization separator element 300 which is not rotated by 90degrees, dip is seen in any of the cases in which the continuous opticaloutput is set to 3.5 mW, 3.0 mW, and 2.5 mW, and the depth of dip islarge when the continuous optical output is set to a large value, and itis shifted to the low wavelength side.

The etching rate of ZnS, SiO2 and Zn (the molar ratio: 64:13:33) tohydrofluoric acid of 2% by weight is measured. In the non annealingcase, the etching rate is about 5.26 nm/second. In the case in whichannealing is performed using an electric furnace (air atmosphere) for 30minutes at 500 degrees C., the etching rate is about 0.17 nm/second.This result shows that the etching rate ratio (the ratio of thenon-annealing case to the annealing case) by the performance ofannealing is about 33, and etching resistance improves rapidly byannealing.

As for the laser beam irradiation and the annealing, the finaltemperature and the highest temperature attainment time are differentbut they are consistent in that heat is supplied. For this reason, inthe embodiment 17, supply of heat by laser beam 306 is mentioned as oneof the factors to which pattern formation of the mixed material layer304 is carried out by being immersed in a hydrofluoric acid 307 andetching after irradiating laser beam 306.

Also when the same experiment is conducted using ZnS—SiO2 (the molarratio: 80:20), the almost same etch selectivity is obtained, andcrystallization of ZnS is conjectured that such an etching resistancechange originates greatly.

When the thin film which is formed of ZnS, SiO2 and Zn was annealed for30 minutes at 500 degrees C. among the atmosphere, the transmittance inthe visible light region increased and the diffraction X-ray peak of ZnOwas seen from X-ray diffraction. That is, oxidization of Zn is checked.For this reason, it is surmised also in mixed material layer 304 laserbeam 306 was irradiated that Zn has oxidized.

Namely, if the mixed material layer 304 is irradiated 306, Zn which hasoptical absorption ability will absorb laser beam 306, and it oxidizesand the transmittance in the visible light region of the minutestructure 306 increases. At this time, since it is transparent in thevisible light region, when ZnS and SiO2 glare laser beam 306, patternformation of the transparent material is carried out.

The light transmittance of the sample in which the 100-nm-thick ZnSlayer was formed on the glass substrate whose light transmittance is 93%was about 20%, about 60%, and about 90% in wavelengths in 300 nm, 405nm, and 550 nm, respectively.

On the other hand, the light transmittance of SiO2 exceeds 90% in a200-1700 nm wavelength zone. At this time, pattern formation of ZnS—SiO2(the molar ratio: 80:20) can also be carried out by irradiating thelight which ZnS—SiO2 (the molar ratio: 80:20) absorbs, for example, theDUV (deep ultraviolet) laser beam whose wavelength is 266 nm, and theEUV (extreme ultraviolet) laser beam whose wavelength is 13.5 nm.

However, the equipment becomes expensive and irradiation time is alsorequired, so that the wavelength of the laser beam to glare becomesshort. In the embodiment 17, since the optical absorption ability of amixed material layer is raised and the vacuum is not needed, minutestructure is producible by irradiating the semiconductor laser beamwhose visible regions, for example, a wavelength, are 405 nm, 650 nm,and 780 nm. Such a polarization separator element 300 can be used alsoas a diffraction grating.

Embodiment 18

The optical filter shown in FIG. 38 was produced. As for optical filter400, ZnS layer 402 is formed on polycarbonate substrate 401, and minutepoint-like structure 403 is periodically formed on it. For this reason,it has the function to reflect P polarized light 411 or S polarizedlight 412 to light 410 of a specified wavelength according to thecharacteristics (a period, a refractive index) of optical filter 400.

The method of manufacturing the optical filter 400 is shown in FIG.39A-39D. First, 20 nm in height and unevenness (land groove) of pitch400 nm manufactured polycarbonate substrate 401 with a thickness of 0.6mm formed in the shape of a concentric circle according to the processof the common optical disc of having used master substrate and astamper, and an injection molding.

Next, a mixed material layer 404 with a thickness of 200 nm which isformed of 10-nm-thick ZnS layer 402, and ZnS, SiO2 and Zn (the molarratio: 64:13:33) on polycarbonate substrate 401 in order It formed by RFsputtering using a sputtering apparatus CFS-8EP-55 (from ShibauraMechatronics Co.) (refer to FIG. 39A).

A blue laser light 406 whose wavelength by which NA of laser beamirradiation equipment (made by Shibasoku Co.) was focused with objectivelens 405 of 0.85 is 405 nm. The focus was carried out to the surface ofmixed material layer 404 by which tracking was carried out, and pulsedlight irradiation was performed on it with 10 mW pulsed light output topolycarbonate substrate 401 to rotate (refer to FIG. 39B).

Then, after being immersed in a hydrofluoric acid 407 for 10 seconds 2%by weight and etching (refer to FIG. 39C), it was made to wash and drywith pure water, and minute structure 403 obtained optical filter 400arranged periodically (refer to FIG. 33D). At this time, mixed materiallayer 404 laser beam 406 was fully irradiated remains, and it becomesminute structure 403. The gap of minute structure 403 in the trackdirection is about 400 nm.

The scanning electron microscope photographs of the optical filter 400are shown in FIG. 40A and FIG. 40B. The photographs of FIG. 40A and FIG.40B are taken from the top surface direction and the slanting direction,respectively.

By entering S polarized light 412 in the optical filter 400 and thepolycarbonate substrate 401, the wavelength dependency to S polarizedlight was measured as shown in FIG. 41. Similarly, by entering Spolarized light 412 in the optical filter 400 which was rotated 90degrees, the wavelength dependency to S polarized light was measured. Inthe measurement, a high-speed spectroscopic ellipsometer M-2000DI (fromJ. A. Woollam Japan) was used as a measuring device, the measurementspot diameter was about 3 mm, and the measurement was performed in themode of transmittance measurement using linear polarization.

When it is optical filter 400 which 674 nm and 701 nm are made into acenter wavelength in the case of optical filter 400 which is not rotated90 degrees, and narrow dip of line width is comparatively looked at, andwas rotated 90 degrees from FIG. 41, it turns out that dip is seen bymaking 655 nm into a center wavelength. Therefore, optical filter 400has a function which filters polarization of a specific wavelength zone.At this time, reflection factor measurement shows that the lightcorresponding to a dip wavelength which is not penetrated is reflected.

Next, except having changed the pulsed light output of laser beam 406,when optical filter 400 was produced like the above, the tendency forthe depth of dip of the one where a pulsed light output is larger tobecome deep was seen. Pattern formation of the transparent material iscarried out by irradiating laser beam 406 as in the embodiment 17 alsoin this case.

Embodiment 19

As an example of a light emitting device, inorganic electroluminescence(EL) elements 500A and 500B shown in FIG. 42A and FIG. 42B wereproduced. In an EL element, luminescence occurs by the recombination ofa positive hole and an electron. Although a flat substrate is usuallyused in an EL element, if the substrate in which the uneven pattern isformed is used, the incident light of under a critical angle will bepenetrated according to the acid resisting effect, and the incidentlight exceeding the critical angle which cannot be taken out can usuallybe taken out as diffracted light. As a result, the optical extractionefficiency is increased to about 1.5 times.

The inorganic EL element 500A includes the polarization separatorelement 300 (diffraction grating) in which the ZnS layer 302 is formedon the polycarbonate substrate 301, and linear minute structures 303 areperiodically formed on the ZnS layer 302. On the surface of thepolycarbonate substrate 301 where no minute structure 303 is formed, thecathode 501 which is formed of ITO (Indium tin oxide), the luminescentlayer 502 which is formed of ZnS—Mn (the percentage of content of Mn isseveral percents by weight), and the anode plate 503 which is formed ofAl are laminated sequentially in this order.

Similar to the inorganic EL element 500A, the inorganic EL element 500Bhas a diffraction grating, and the cathode 501, the luminescent layer502, and the anode plate 503 are laminated on the minute structures 303sequentially in this order.

In this embodiment, each minute structure 303 has a high transmittancein the visible light region, and it is suitable as a material whichconstitutes an EL element.

If a direct current voltage or alternating voltage is applied betweenthe cathode 501 and the anode plate 503, a yellow-orange luminescence(the center wavelength: 585 nm) is seen and, in each case of theinorganic EL elements 500A and 500B, the luminous efficiency (opticalextraction efficiency) is increased from that in the case where nominute structure 303 is formed.

In the embodiment 19, ZnS—Mn was used for the luminescent layer 502, butthe invention is not limited to this embodiment. Alternatively, anyother luminescent materials, such as CaSSe—Eu, CaS—Eu, SrS, Cu, SrS—Ce,BaAl2S4—Eu, BaZnS3—Mn, and ZnMgO, may be used.

Moreover, an organic EL device may be formed by using organicluminescent materials, such as a phenylene-vinylene base and an arylenebase, for the luminescent layer 502, and using supply of a directcurrent voltage.

Embodiment 20

As an example of a photoelectric transducer, the dye-sensitized solarcell 600 shown in FIG. 43 was produced. A photoelectric transducer has aphotoelectric conversion layer which absorbs light and transforms itinto electricity. The amount of light absorbed increased as thethickness of the photoelectric conversion layer increases. Thephotoelectric conversion layer formed of a Si semiconductor or anorganic semiconductor has a photovoltaic effect. If the p-n junctionpart or the Schottky junction part is irradiated by an excited light,the resulting electrons and positive holes are separated from each otherby the electric field of the interface, and a potential difference isgenerated therebetween.

Usually, a flat substrate is used for a photoelectric transducer. If thesubstrate in which the uneven pattern is formed is used, the multipathreflection within the photoelectric conversion layer is increased andthe photon inclusion effect is raised. As a result, the photoelectricconversion efficiency is increased by 3% to 5%.

Similar to the embodiment 17, in the dye-sensitized solar cell 600, thelinear minute structures 602 are formed on the flat glass substrate 601,and the cathode 603 is further formed on the minute structures 602.

The photoelectric conversion layer 606 is interposed between the anodeplate 605, formed on the glass substrate 604, and the cathode 603.Coloring matter, titania, an electrolyte, and a redox pair are containedin the photoelectric conversion layer 606.

As the coloring matter, RuL2(NCS)2 (L=4,4′-dicarboxy-2,2′-bipyridine)which is a ruthenium complex is used in this embodiment. However, theinvention is not limited to this embodiment. Alternatively, anothercoloring matter, such as a porphyrin base or a cyanine base, may be usedinstead.

As the titania, its particulates whose particle diameter is about 10-30nm are used in this embodiment. X Line diffraction to the titaniaparticulates showed that they are mostly of anatase type. The titaniamay be formed by the sputtering method. If amorphous is contained andthe photoelectric conversion efficiency is decreased. To avoid this, itis preferred to use particulates with a high degree of crystallinity.

As the electrolyte and the redox pair, the electrolytic solutionIodolyte TG 50 for low-output cells (from Solaronix Co.) (in which 0.5Mof lithium iodide (LiI) and 0.05M of metal iodine (I2) are added topolyethylene glycol of molecular weight 220) is used in this embodiment.However, the invention is not limited to this embodiment. As theelectrolyte, anions, such as lithium ion, and cations, such as chlorideion, may be used. As the redox pair, any of an iodine-iodine compound, abromine-bromine compound, etc. may be used.

In the photoelectric conversion layer 606, the coloring matter absorbslight to emit electrons, and the titania (TiO2) of the semiconductorreceives the electrons to transfer them to the cathode 603. The holes(h+) remaining in the coloring matter oxidize iodide ions (I−), andtri-iodide ions (I3−) are formed. The I3− are reduced by the anode plate605. Electricity is generated by repeating the above cycles.

As the cathode 603 and the anode plate 605, ITO (indium tin oxide, 5% oftin oxide, 95% of indium oxide) is used in this embodiment. However, theinvention is not limited to this embodiment. Alternatively, an FTO filmin which fluorine is doped to tin oxide may be used.

The minute structures 602 may be produced on a polycarbonate substrate,etc. other than the glass substrates 601 of quartz. However, in aphotoelectric transducer, the temperature is increased to about 500degrees C. when forming ITO, and the glass substrate 701 having goodheat resistance is usually used. The minute structures 602 in thisembodiment contains ZnO.

The minute structures 602 are applicable also to solar cells other thanthe dye sensitizing type solar cells, such as Si thin film solar cell, aCIGS solar cell (Cu(In1-x, Gax)Se2), and a solar cell using acopper-indium-gallium-selenium base material.

Embodiment 21

The aspheric optical lens shown in FIG. 44A and FIG. 44B was produced.FIG. 44A is a perspective view of the aspheric optical lens and FIG. 44Bis a cross-sectional view of the aspheric optical lens. The maximumdiameter is about 2 micrometers, the height is about 2.5 micrometers,the aspheric optical lens 700 is in a configuration near a super-halfsphere, and its maximum diameter is slightly larger than the lensdiameter of the surface in contact with the quartz substrate 701.

The transmittance to the light with the wavelength of 660 nm is about90%, and the aspheric optical lens 700 has a sufficiently availabletransmittance in a visible light region.

The aspheric surface optical lens 700 may be produced in the same manneras in the embodiment 18 except that the flat quartz substrate 701 isused instead of the polycarbonate substrate 401, and the laser beamwhose wavelength is 780 nm is used instead of the blue laser light 506whose wavelength is 405 nm.

From the results of powder X-ray diffraction, it turned out that theaspheric optical lens 700 has a very weak peak of Zn and an intense peakof ZnO. It appears that Zn is mostly oxidized and ZnO is formed.Thereby, the transmittance in the visible light region of the asphericoptical lens 700 increases.

From the results of annealing experiments of a thin film, it wasestimated that the refractive index of the aspheric surface optical lens700 is about 2.2. The aspheric optical lens 700 has a refractive indexhigher than that of quartz and contains an inorganic material, and thereliability is high. The aspheric surface optical lens 700 is able to beproduced on the quartz substrate 701 and easily divided into pieces.

The configuration of the aspheric optical lens 700 is not restrictive.And by changing the pulsed light intensity of laser beam 506 or thethickness of the mixed material layer 504, it is possible to arrange theaspheric optical lens 700 in a hemispherical configuration.

Next, a description will be given of embodiments of the write-onceinformation recording medium of the invention with reference to theaccompanying drawings.

The cross-sectional structure of the write-once optical recording mediumof the embodiment 1 (an example of the write-once information recordingmedium of the invention) is shown in FIG. 45A and FIG. 45B. FIG. 45Ashows the state of the write-once optical recording medium beforerecording by irradiation of a laser beam, and FIG. 45B shows the stateof the write-once optical recording medium after recording by theirradiation of the laser beam. The illustration of FIG. 45A and FIG. 45Bis a schematic diagram, and does not correspond to the actual thicknessor dimensions.

In the write-once optical recording medium of the embodiment 1, thetrack pitch was 0.32 micrometers and the CNR (Carrier to Noise Ratio)was 45 dB with the period of recording marks being 300 nm. The substrate1 is a polycarbonate substrate which has a repetition unevenness oflands and grooves with the track pitch of 0.32 micrometers. On thesubstrate 1, the reflection layer 2 of Ag with the thickness of 40 nm,the lower dielectric layer 3 of ZnS—SiO2 (the molar ratio: 80:20) withthe thickness of 50 nm, the recording layer 4 of ZnS, SiO2 and ZnTe (themolar ratio: 70:20:10) with the thickness of 15 nm, the upper dielectriclayer 5 of ZnS—SiO2 (the molar ratio: 80:20) with the thickness of 40nm, and the protection layer 6 of an acrylic resin of light transmissiontype with the thickness of 100 micrometers are sequentially deposited inthis order.

If the recording layer 4 of the write-once optical recording medium ofthe embodiment 1 is irradiated by a laser beam using the optical pickup,recording marks 7 which are formed by cavities can be formed in therecording layer 4 as shown in FIG. 45B, so that information is recordedin the recording layer 4.

The write-once optical recording medium of the embodiment 1 wasmanufactured as follows. That is, the substrate 1 of polycarbonate whichhas repetition unevenness with the track pitch 0.32 micrometers of landsand grooves was produced through injection molding using a stamper.Next, the reflection layer 2 (Ag, the thickness: 40 nm), the lowerdielectric layer 3 (ZnS—SiO2, the molar ratio: 80:20, the thickness: 50nm), the recording layer 4 (ZnS, SiO2 and ZnTe, the molar ratio:70:20:10, the thickness: 15 nm), and the upper dielectric layer 5(ZnS—SiO2, the molar ratio: 80:20, the thickness: 40 nm) weresequentially deposited in this order on the substrate 1 throughsputtering using a sputtering apparatus CFS-8EP-55 (from ShibauraMechatronics Co.).

Then, the spin coating of the acrylic resin was carried out on thedielectric layer 5, the hardening by UV irradiation was performed, andthe protection layer 6 (of light transmission type, the thickness: 100micrometers) was formed.

Recording and reproduction of the write-once information recordingmedium of the embodiment 1 are performed as follows. Namely, a bluelaser beam (the wavelength: 405 nm) is focused by the objective lens 12(lens NA: 0.85) of the laser beam irradiation apparatus having theoptical pickup as shown in FIG. 48B, on the surface of the recordinglayer 4. The focusing is carried out from the protection layer 6 side,the laser beam is multi-pulse modulated in accordance with thepredetermined recording strategy (the emission-waveform control of thelaser beam at the time of recording), and random data is recorded in therecording layer 4.

Similarly, the information is reproduced from the recording medium usingthe optical pickup by continuous irradiation of the laser beam (thewavelength: 405 nm) and the reproduction signal is observed. In thismanner, the information based on the random data recorded in therecording layer 4 of the write-once optical recording medium of theembodiment 1 is reproduced, and the function and performance of thewrite-once optical recording medium of the embodiment 1 is checked.

The cavity and the expansion are observed in the area where therecording marks are formed in the recording layer 4 of the write-onceoptical recording medium after recording when the surface configurationis checked using the atomic force microscope (AFM).

The expansion contains minute cavities inside it. Each of the cavity andthe expansion arises after the recording is performed by irradiating therecording layer 4 by the laser beam, and due to the existence of thecavity and the expansion, the reflection factor of the recording layer 4is changed before and after the recording. And it was confirmed that theinformation based on the above-mentioned random data is recorded in therecording layer 4 and that this information is reproducible.

The following experiments were conducted in order to observe the cavityand the expansion existing in the recording marks formed in therecording layer 4 of the write-once optical recording medium of theembodiment 1.

Namely, the sample being observed is formed as follows. The recordinglayer 4 of ZnS, SiO2 and ZnTe (the molar ratio: 70:20:10, the thickness:40 nm) is formed on the substrate 1 of polycarbonate by sputtering usinga sputtering apparatus CFS-8EP-55 (from Shibaura Mechatronics Co.). Andthe pulsed laser irradiation (the wavelength: 405 nm, the objective lensNA: 0.85) is performed to the recording layer 4 of this sample. Thepulses laser irradiation is performed at intervals of 400 nm, and thelinear velocity is 4.5 m/sec.

The scanning electron microscope (SEM) photographs of the recordingmarks formed in the surface (the recording layer 4) of the sample atthis time are shown in FIG. 46A and FIG. 46B. In the state of thewrite-once optical recording medium, the protection layer 6 is laminatedon the recording layer 4, and observation of the surface state of therecording layer 4 is difficult. In the experiments, the above-mentionedsample is prepared and the recording marks which are formed in therecording layer 4 are observed.

FIG. 46A shows a SEM photograph when the irradiation intensity of thelaser beam is 6 mW, and FIG. 46B shows a SEM photograph when theirradiation intensity of the laser beam is 7 mW.

In the case of FIG. 46B, the holes 9 with the diameter of about 80 nmare formed at almost all the laser beam radiation portions. In the caseof FIG. 46A, the laser irradiation portions 8 are in an expansion state,and the cavities are formed inside the laser irradiation portions 8.These states were similarly observed by the AFM measurement or thetransmission electron microscope (TEM).

It is estimated that the expansion (state) and cavity have contributedto the reflection factor change in the write-once information recordingmedium of the invention. Although the spot diameter of the laser beam isabout 400 nm, the write-once information recording medium of theinvention is advantage in that holes with the diameter of 80 nm that issufficiently smaller than the spot diameter can be formed.

The mixed inorganic material which constitutes the recording layer 4 inthe write-once information recording medium of the embodiment 1 containsZnS (zinc sulfide) as a sulfur compound of the material A, contains SiO2(silicon dioxide) as a silicon oxide of the material B, and containsZnTe (zinc telluride) as the material C. The light transmittance ofZnS—SiO2 (the molar ratios: 50:50-90:10) with the thickness of 15 nmwhich is the same as the thickness of the recording layer 4 in thewrite-once information recording medium of the embodiment 1 is about100%. That is, the ZnS—SiO2 is equivalent to the mixed inorganicmaterial, constituting the recording layer 4, from which the ZnTe whichis the material C is excluded. This shows that the light transmittancein the visible light region of the ZnS—SiO2 falls by adding ZnTe whichis the material C thereto.

Specifically, when the light transmittance in the visible light regionis compared between the layer formed of ZnS—SiO2 (material A andmaterial B) and the layer formed of ZnS, SiO2 and ZnTe (the mixedinorganic material: material A, material B, and material C) with respectto the same thickness, it turned out that the whole transmittance falls(which falls to 60% from 100%) as the content ratio of ZnTe increases,but the optical absorption ability increases (the extinction coefficientk increases from the order of 10⁻¹ to the order of 10⁻³). The opticalabsorption ability was measured using the spectroscopic ellipsometer.

The extinction coefficient k of the ZnS—SiO2 (the molar ratio: 80:20) isabout 1×10⁻³ on the wavelength of 405 nm. On the other hand, theextinction coefficient k of the recording layer 4 formed with the mixedinorganic material is about 1×10⁻¹ on the wavelength of 405 nm.Therefore, in the embodiment 1, as a result of adding the material C tothe recording layer, it turned out that the extinction coefficient k canbe made to about 1×10⁻¹, and it is possible to make the absorption of ablue semiconductor laser beam easy. The extinction coefficient k wasmeasured using the spectroscopic ellipsometer (from J. A. Woollam Japan,VASE).

In the write-once information recording medium of the embodiment 1 shownin FIG. 45A and FIG. 45B, the recording layer 4 is inserted between thelower dielectric layer 3 and the upper dielectric layer 5. In contrast,in the write-once information recording medium of the embodiment 2 shownin FIG. 47A and FIG. 47B, the lower dielectric layer 3 and the upperdielectric layer 5 do not exist, but the recording layer 4 is formed onthe substrate 1, and the protection layer 6 is directly formed on therecording layer 4. The thickness of the recording layer 4 in theembodiment 1 was 15 nm, but the thickness of the recording layer 4 inthe embodiment 2 is changed to 40 nm.

FIG. 47A is a plan view of the write-once information recording mediumof the embodiment 2, and FIG. 47B is a cross-sectional diagram of thewrite-once information recording medium of the embodiment 2.

The write-once information recording medium of the embodiment 1 has thecomposition in which the recording layer 4 is interposed between thelower dielectric layer 3 and the upper dielectric layer 5, and isexcellent in reliability compared with the write-once informationrecording medium of the embodiment 2. Similar to that of the write-onceinformation recording medium of the embodiment 1, the write-onceinformation recording medium of the embodiment 2 is checked as towhether recording and reproduction of the information based on therandom data in the recording layer 4 can be performed. As a result ofthe checking, it turned out that the recording and reproduction can beperformed similar to the write-once information recording medium of theembodiment 1.

In the embodiment 3, the master substrate for optical informationrecording media (disk) was produced. The plan view of the mastersubstrate produced in the embodiment 3 is shown in FIG. 48A. As shown inFIG. 48A, the recording pits 11 are formed on the thin film 10. Thetrack pitch is 0.32 micrometer and the shortest pit size is 150 nm. Thesubstrate used is the quartz substrate.

If the master substrate of quartz obtained in the embodiment 3 is used,a stamper for optical disc injection molding and an optical informationrecording medium can be produced.

Next, the method of manufacturing the master substrate of FIG. 48A willbe explained with reference to FIG. 48B.

FIG. 48B is a cross-sectional diagram showing the master substrate. Therecording pits 11 (concave pattern (holes or indentations)) are formedwhen the thin film 10 which is the pattern formation layer formed on thequartz substrate 14 is irradiated by the laser beam 13 which is focusedusing the objective lens 12.

The method of manufacturing the master substrate will be explained.First, the quartz substrate with high surface accuracy was prepared.Then, RF sputtering is performed using the sputtering apparatusCFS-8EP-55 (from Shibaura Mechatronics Co.) to form the patternformation layer of ZnS, SiO2 and Zn (the mixed inorganic material, themolar ratio: 54:13:33) of the substrate. The thickness of the patternformation layer is about 40 nm. It is the pattern formation layer beforea fine pattern is formed.

Next, as shown in FIG. 48B, using the objective lens 12 (lens NA: 0.85)of the laser beam irradiation apparatus LA330 (from Shibasoku Co.), theblue laser beam 13 (wavelength: 405 nm) is focused on the patternformation layer. The laser beam is multi-pulse modulated, and the laserbeam irradiation is performed so that random data is recorded in therecording layer.

The hole-like pits (concave pattern) are formed at the laser irradiationportions of the pattern formation layer according to this process. Bythe atomic force microscope (AFM) and the scanning electron microscope(SEM), the formation of the pits was also confirmed. The depth of thepits is about 40 nm. This corresponds to the thickness of the patternformation layer formed of the mixed inorganic material. In themeasurement using the ellipsometer VASE (from J. A. Woollam Japan), theextinction coefficient k of the pattern formation layer formed of themixed inorganic material was about 1×10⁻¹.

The quartz substrate in which the pits are formed in the patternformation layer can be used as a master substrate of a stamper foroptical disc injection molding.

Next, based on the master substrate of the embodiment 3, Nielectroforming was performed and Ni stamper was actually produced. Then,the BD-ROM substrate was produced by injection molding or 2P transfer(Photo-Polymerization) using the Ni stamper.

In the above case, the Ni electroforming was performed, and it installsin RIE (Reactive Ion Etching) equipment, and etching by CF4 gas isperformed, and Ni electroforming may be performed after making formreflect on the quartz substrate. The section of quartz substrate 14 inwhich the recording pits 15 are formed in the quartz surface is shown inFIG. 49.

The recording pit 15 was formed in the pattern formation layer formed byZnS, SiO2 and Zn (the mixed inorganic material, material A, material Band material C). The quartz substrate 14 of FIG. 49 was producible, whenRIE etching and hydrofluoric acid removed this pattern formation layer(SiO2 is etched with hydrofluoric acid) and a residue removed furtherusing argon gas.

The master substrate for optical information recording media wasproduced. The surface schematic diagram of a master substrate is shownin FIG. 48A. As shown in FIG. 48A, recording pit 11 is formed on thinfilm 10. The track pitch is 0.32 micrometer and the shortest pit size is150 nm. The substrate material is quartz. The master substrate made fromquartz origin a stamper for optical disc injection moldings an opticalinformation recording medium is further producible.

The method of manufacturing the master substrate of FIG. 48A will beexplained with reference to FIG. 48B. FIG. 48B is a cross-sectionaldiagram.

The recording pits 11 are formed by irradiating the thin film 10(pattern formation layer) on the quartz substrate 14 by the laser beam13 which is focused with the objective lens 12.

First, the quartz substrate with high surface accuracy was prepared.Then, it is RF sputtering about the pattern formation layer formed usinga sputtering apparatus CFS-8EP-55 (from Shibaura Mechatronics Co.) byZnS, SiO2 and AgInSbTe (the mixed inorganic material, the molar ratio:54:13:33).

On the quartz substrate, it formed by a thickness of 40 nm. This layerwas used as the pattern formation layer. The composition ratio ofAgInSbTe is 6:0.7:25.1:68.2 (Ag₆In_(0.7)Sb_(25.1)Te_(68.2)). In thefollowing, it is referred to as AgInSbTe, for the sake of convenience.

Next, as shown in FIG. 48B, the blue laser beam 13 (the wavelength: 405nm) is focused with the objective lens 12 (lens NA: 0.85) of the laserbeam irradiation equipment and applied to the pattern formation layer,and the laser beam is multi-pulse modulated so that the random data isrecorded.

The hole-like pits (concave pattern) are formed in the laser irradiationportions of the pattern formation layer of this process. Checkingformation of this pit (concave pattern) with the atomic force microscope(AFM) and the scanning electron microscope (SEM), the depth is about 40nm and was equivalent to the thickness of the pattern formation layer.The extinction coefficient k of the pattern formation layer formed ofthe mixed inorganic material was about 1×10⁻¹.

Thus, the quartz substrate in which the pit was formed can be used as amaster substrate of a stamper for optical disc injection moldings. Ni(nickel) electroforming was actually performed based on the mastersubstrate by the invention, and Ni stamper was produced. Then, theread-only medium (ROM) was produced by injection molding or 2P transfer(photo-polymerization) using the Ni stamper.

In this embodiment, AgInSbTe was used as the material C which is theadded mixture to (ZnS) of the material A and (SiO2) of the material B.The AgInSbTe is the 4 element-based mixture of inorganic material. Thehole (pit) can be formed in the pattern formation layer and the mastersubstrate can be produced by this material C. Accordingly, if thematerial (inorganic material of a metal, a semimetal, or asemiconductor) which adds the optical absorption ability is used as thematerial C and the irradiation conditions of the laser beamcorresponding to the optical absorption ability in the mixed inorganicmaterial are chosen suitably, the production of the master substrate ispossible.

The master substrate for optical nonreflection films (anti-reflectionfilms) is produced. The schematic diagrams of the master substrate foroptical nonreflection films are shown in FIG. 50A and FIG. 50B. FIG. 50Ais a top view of the master substrate in which the pattern including theperiodical structure of circular pits 17 is schematically shown. FIG.50B is a cross-sectional diagram of the master substrate.

The period is about 300 nm, the cavity diameter is about 80 nm, and thefilm thickness is about 20 nm. The substrate is a quartz substrate andthe pattern formation layer 16 of the mixed inorganic material isformed.

The materials (the mixed inorganic material) of the periodical structurein the pattern formation layer 16 formed on the quartz substrate 18 areZnS, SiO2 and Zn (68:17:15).

When compared with a quartz substrate of the same thickness in which theperiodical structure is not formed, the transmittance to the light withthe wavelength in a range of 400-600 nm is increased, and it is possibleto produce a master substrate on which an optical nonreflection filmattaining nearly 100% nonreflection is formed. This is because theperiodical structure by the minute structure turns into the moth-eyestructure, which controls the reflection and makes the incident lightpenetrate.

Although it is possible to use the master substrate itself as an opticalnonreflection film, the reproduction of many optical nonreflection filmsthrough Ni electroforming by using it as the master mold is suitable forvolume production. The optical nonreflection film is used for polarizingplates, such as a rear projection screen and a projector display, asolar cell, etc.

The manufacturing method will be explained. First, on the quartzsubstrate 18, a thin film 16 (pattern formation layer) of ZnS, SiO2 andZn (the molar ratio: 68:17:15) is formed. After forming the thin film,it is placed on the XY stage and the thin film 16 (pattern formationlayer) is irradiated by the blue laser beam (the wavelength: 405 nm)which is focused using the objective lens (NA: 0.85).

The periodic pits are formed by irradiating it by the pulsed light atgiven intervals (the period: 300 nm, the laser power: 11 mW). After themaster substrates are produced with the wafer, it is divided into piecesof several millimeter square by dicing, and rinsing is performed toremove impurities therefrom.

FIG. 51 is a cross-sectional diagram of the quartz substrate 18 to whichetching is performed using the quartz substrate having the patternformation layer in which the periodic pits are formed.

The pattern 19 is formed on the quartz substrate 18. The film of themixed inorganic material which is formed in the pattern can be used asan optical nonreflection film. However, when the materials of thesubstrate and the material of the thin film differ from each other, theeffect as the optical nonreflection film may fade and exfoliation mayarise at the tome of a next dicing process. To avoid the problem, thefilm of the mixed inorganic material is etched to the quartz substrate18, and copying of the pattern is performed by transferring the pits(pattern) to the quartz substrate.

The configuration of the pattern 19 (pits) formed on the surface ofquartz substrate 18 is quite near the configuration of the structure ofZnS, SiO2 and Zn (the molar ratio: 68:17:15) which is used as the mask(resist).

In this case, the etching rate of the structure of ZnS, SiO2 and Zn (themolar ratio: 68:17:15) to CF4 is small enough, and the configuration ofa high aspect ratio (the vertical length is large than the horizontallength) is producible.

FIG. 52A and FIG. 52B show scanning electron microscope photographs ofsamples of the optical information recording medium in an embodiment ofthe invention in which a recording layer formed of a mixed inorganicmaterial is irradiated by a laser beam. The mixed target of ZnS, SiO2and Ag (the molar ratio: 72:18:10) is used, sputtering is performed sothat the thin film 20 with the thickness of 40 nm is formed on thesubstrate of polycarbonate, and each sample is irradiated by the laserbeam (the wavelength: 405 nm, NA: 0.85).

In the case of FIG. 52A, the laser power is 8 mW. The expansion parts 21are created in the thin film 20. In the case of FIG. 52B, the laserpower is 9 mW. The holes 22 with the diameter of about 80 nm arecreated. If the material which can form the mixed target is used, themixed target can be produced with any of metals, semimetals andsemiconductors may be used.

ZnO which has a large transmittance to blue laser than other elementsmay be used as the material C, instead of Ag. Specifically, whenZnTe—ZnO is used as the material C and the mixed material of ZnS, SiO2,ZnTe and ZnO (64:18:10:8) is produced and irradiated by the laser beamin the same manner, the holes with the ends being sharp was able to beformed.

It has been confirmed that the pits can be formed also when any of InSb,AgInSbTe, and GeSbTe is used as the material C, instead of Ag, and thelaser beam irradiation is performed.

The write-once information recording medium of the invention isapplicable as write-once recording media including CD-R, DVD-R, HD DVD(High-Definition Digital Versatile Disc), and BD-R (Blu-rayDisc-Recordable). The information recording medium of the invention isalso applicable to a multilayer disc in which two or more recordinglayers are formed in a single optical recording medium in order toincrease the storage capacity. The write-once information recordingmedium of the invention is also applicable to a single-layer disk inwhich tracks with a narrow track pitch are formed within the recordinglayer, in order to increase the storage capacity.

The master substrate of the invention is appropriate for use as mastersubstrates for read-only media (ROM: Read Only Memory) or fornano-imprinting in manufacturing information recording media with lowcost.

The present invention is not limited to the above-described embodiments,and variations and modifications may be made without departing from thescope of the present invention.

The present application is based on and claims the benefit of priorityof Japanese patent application No. 2007-071485, filed on Mar. 19, 2007,Japanese patent application No. 2007-079482, filed on Mar. 26, 2007,Japanese patent application No. 2007-120218, filed on Apr. 27, 2007, andJapanese patent application No. 2007-276730, filed on Oct. 24, 2007, thecontents of which are incorporated by reference in their entirety.

What is claimed is:
 1. An optical recording medium, comprising: asubstrate; a light absorption layer on the substrate; and a minutestructure on the light absorption layer, wherein the substrate, thelight absorption layer, and the minute structure are arranged in theorder recited, wherein the minute structure is a recording mark and theminute structure comprises: a sulfur compound; a silicon oxide; and amaterial for raising an optical absorption ability to a light with apredetermined wavelength, wherein the molar percentage of the siliconoxide in the minute structure is in the range of between 10 mol % and 30mol %, wherein the minute structure has a diameter in the range of80-450 nm, wherein the material for raising the optical absorptionability to the light with the predetermined wavelength comprises: atleast one of ZnTe, ZnSe or MnS; and a fluorescent material, and whereinthe minute structure is a mixture of the sulfur compound, the siliconoxide, and the material for raising the optical absorption ability tothe light with the predetermined wavelength.